• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention is a urea-urethane compound represented by the following formula; A process for preparing the compound; Developing agents containing urea-urethane compounds; And colorless or light colored leuco dyes. [Wherein, R represents a residue such as an aliphatic compound; A 1 and A 2 each represent a residue such as an aromatic compound; Each residue may have a substituent].
    公开号:KR20030007444A
    申请号:KR1020027011356
    申请日:2001-03-01
    公开日:2003-01-23
    发明作者:가바시마가즈오；고바야시히로시；이와야데쯔로
    申请人:아사히 가세이 가부시키가이샤；
    IPC主号:
    专利说明:

    New colorants and recording materials {NOVEL COLOR FORMER AND RECORDING MATERIAL}
    [3] Various chemical color development systems using recording energy such as heat and pressure are known. Among these systems, a color development system consisting of a colorless or pale color dye precursor, and a two-component color development system composed of a color developer capable of developing color upon contact with the dye precursor has been known from the early days, and has been widely known in recording materials. It is used. For example, there are a pressure-sensitive recording material that records using pressure, a thermal recording material that uses heat, and a photosensitive recording material that uses light.
    [4] Pressure-sensitive recording materials have generally been used in paper-like plates. Generally, the pressure-sensitive recording material is obtained by dissolving the dye precursor in a suitable solvent, emulsifying the obtained solution to several microns, and then microencapsulating the emulsion. A first layer of paper obtained by applying the microcapsules to a support (also referred to herein as a top sheet), and a second layer of paper obtained by applying a developer layer containing a developer to another support ( Also referred to herein as the bottom sheet) is superimposed so that the surface to which the microcapsules are applied and the surface to which the developer is applied face to each other. When pressure is applied to the obtained assembly at a pen pressure, squeeze pressure, or the like, the microcapsules are broken to release the contents containing the dye precursors. The dye precursor moves to the developer layer and contacts the developer, whereby a color reaction occurs to obtain an image.
    [5] In recent years, for example, in various information apparatuses such as a facsimile machine, a printer, a recorder, and the like, a thermal recording method in which recording is performed by thermal energy is frequently employed. The thermal recording material used in the thermal recording method has many excellent characteristics such as high whiteness, appearance and feel similar to ordinary flat paper, and good recording aptitude such as high color development sensitivity. The thermal recording method has the advantage that, for example, the apparatus used in the present method is compact, maintenance is unnecessary, and noise is not generated. Therefore, the use range of the thermal recording method is expanding in a wide range of fields such as measurement recorders, fax machines, printers, computer terminals, labels, and vending machines for train tickets.
    [6] In the thermosensitive recording method, a recording material obtained by forming a chromophoric layer containing a two-component color developing composition on a support is mainly used, and the components of the heat-sensitive composition include the heat-sensitive recording material as a thermal head, a high temperature stamp, Coloring and recording are performed in contact with each other by treating the recording material with heat supplied as recording energy in laser light or the like. Many of the compositions used as chromophoric compositions are those obtained by using colorless or pale, electron donating dye precursors (particularly leuco dyes), and acidic developer such as phenolic compounds. One example of a recording material obtained using the dye precursor is a thermal paper obtained by using a combination of crystal violet lactone and 4,4'-isopropylidenediphenol (bisphenol A) as a thermochromic composition. (See US Patent No. 3539375, et al.).
    [7] As the dye precursor and the developer used in each of the above recording methods, mainly an electron donating compound and an electron accepting compound are used, respectively. This is because an electron donating compound and an electron accepting compound have excellent properties such as dye precursors, which are electron donating compounds, and a colorant, which is an electron accepting compound, to instantaneously obtain a high color development image; This is because the appearance close to white can be obtained and red, orange, yellow, green, blue, black and the like can be obtained. However, the color development image obtained is very poor in chemical resistance, so that, when contacted with a plasticizer contained in a plastic sheet or rubber, or a chemical contained in food or cosmetics, the recording is easily lost. In addition, the color image is very poor in recording storage stability, so that even when exposed to sunlight for a relatively short time, the recording may be faded or further lost. Therefore, the color development compositions containing the dye precursors and the developer have been severely limited in their use, and their improvement is strongly demanded.
    [8] In recent years, a phenolic compound represented by bisphenol A is considered to be an environmental hormone and is not suitable for use. Therefore, a nonphenolic developer is preferable.
    [9] In order to meet the above demands, for example, JP-A-59-115887 and US Pat. No. 45,21793, recording materials having high storage stability, contain a combination of an aromatic isocyanate compound and a coloring composition containing an imino compound. A recording material is disclosed. The above-mentioned reference discloses various recording materials in which two kinds of color-forming compositions are contacted and reacted by applying recording energy such as heat, pressure, light, and the like. The reference describes the fact that various shades, such as red, orange, yellow, light brown, dark brown and the like, can be developed by appropriately selecting a chromogenic composition. However, in the invention disclosed in the reference, since the development of black color is still insufficient, the development of black color is strongly desired in the case of a recording material currently commonly used.
    [10] JP-A-8-2111 and JP-A-8-2112 are heat-sensitive recording materials obtained by using a non-phenolic developer, and are heat-sensitive having a colorless or pale dye precursor, and a coloring layer containing a urea compound. The recording material is disclosed. However, the recording material has a low color development density and insufficient storage stability.
    [11] JP-A-5-116459 discloses a thermosensitive recording material having a colorless or pale dye precursor and a thermochromic layer containing a sulfonylurea compound. However, the recording material has low whiteness and insufficient storage stability.
    [1] The present invention relates to novel urea-urethane compounds. The present invention also relates to a novel color development composition obtained using the urea-urethane compound, and a recording material obtained using the color development composition.
    [2] The color development composition of the present invention is useful as a color development composition for recording materials that uses recording energy such as heat, pressure, and the like. The present invention is particularly capable of improving the storage stability of uncolored portions (the original recording material surface) and the color image. The present invention relates to a color developing composition and a recording material, and in particular to a thermal recording material obtained using the color developing composition.
    [12] The present invention relates to the provision of novel urea-urethane compounds or urea-urethane compositions which, when used as a developer for color development compositions, exhibit excellent performance characteristics.
    [13] In addition, the present invention provides a novel color composition and recording material excellent in image preservation and color density by using any of various urea-urethane compounds or urea-urethane compositions, in particular, thermal recordings obtained using the color composition described above. It is about the material.
    [14] The present invention also relates to a urea-urethane compound or urea-urethane composition, and a novel color development composition having further improved performance characteristics by incorporating various additives into a dye precursor, and a recording material obtained using the color development composition. will be.
    [15] The inventors have intensively studied the synthesis of various compounds for chromophoric compositions, and have found that certain compounds exhibit surprisingly good performance characteristics, thus completing the present invention. In addition, the inventors have found that certain compounds are combined with certain dye precursors to exhibit surprisingly good performance characteristics, thus completing the present invention.
    [16] That is, the present invention is as follows.
    [17] A first aspect of the present invention relates to a urea-urethane compound represented by the following formula (c) and having a molecular weight of 5000 or less:
    [18]
    [19] [Wherein R is an aliphatic compound residue,
    [20] A 1 and A 2 are independently aromatic compound residues,
    [21] The nitrogen atom of the urea group is directly bonded to the carbon atoms of the aromatic rings of A 1 and A 2 , respectively,
    [22] R, A 1 and A 2 may have one or more substituents.
    [23] A second aspect of the present invention relates to a urea-urethane compound represented by the following formula (d):
    [24]
    [25] [Wherein R is an aliphatic compound residue,
    [26] Hydrogen atoms of each benzene ring include aromatic compound residues, aliphatic compound residues, heterocyclic compound residues, hydroxyl groups, nitro groups, nitrile groups, carbamoyl groups, sulfamoyl groups, carboxyl groups, nitroso groups, amino groups, May be substituted with an oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom,
    [27] R may have one or more substituents.
    [28] A third aspect of the present invention relates to a urea-urethane compound represented by the following formula (e) or (f), having one or more urethane groups and one or more urea groups in total of 3 or more and 10 or less, and having a molecular weight of 5000 or less:
    [29]
    [30] [Wherein R is an aliphatic compound residue,
    [31] Y is an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue,
    [32] α 1 is an aromatic, heterocyclic or aliphatic compound residue different from Y and having two or more valences,
    [33] n is an integer of 2 or more,
    [34] Each residue may have one or more substituents; or
    [35]
    [36] [Wherein, Z 1 and Y are independently an aromatic compound residue or a heterocyclic compound residue,
    [37] β 1 is an aliphatic compound residue having a valency of 2 or more,
    [38] n is an integer of 2 or more,
    [39] Each residue may have one or more substituents.
    [40] A fourth aspect of the invention relates to a urea-urethane compound, characterized by the following formula g or h:
    [41]
    [42] [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group. Can be substituted with an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom,
    [43] β 1 is an aliphatic compound residue having a valency of 2 or more,
    [44] n is an integer of 2 or more,
    [45] Each residue may have one or more substituents; or
    [46]
    [47] [Wherein R is independently an aliphatic compound residue,
    [48] The hydrogen atom of each benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue,
    [49] Each residue may have one or more substituents,
    [50] γ 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C ( CF 3 ) 2- , -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2), and a group consisting of any group represented by the following formula a The group is selected from or does not exist:
    [51]
    [52] ].
    [53] A fifth aspect of the present invention relates to a urea-urethane composition comprising a urea-urethane compound and a diluent.
    [54] A sixth aspect of the present invention relates to the urea-urethane composition according to the fifth aspect of the present invention, wherein the diluent is a urea compound and / or a urethane compound.
    [55] A seventh aspect of the present invention relates to a urea-urethane composition according to the fifth aspect of the present invention, wherein the diluent is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound.
    [56] Eighth of the present invention is a urea-urethane composition obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound,
    [57] A urea-urethane composition having at least one urea group and at least one urethane group in a molecular structure in total and containing at least 50% by weight of a urea-urethane compound having a molecular weight of 5000 or less.
    [58] A ninth aspect of the present invention relates to a urea-urethane composition according to the eighth aspect of the present invention, wherein the hydroxy compound is a phenol compound.
    [59] A tenth aspect of the present invention relates to a urea-urethane composition according to the eighth aspect of the present invention, wherein the hydroxy compound is an alcohol compound.
    [60] The eleventh aspect of the present invention relates to the urea-urethane composition according to any one of the eighth to tenth aspects of the present invention, wherein the amino compound is an aromatic amino compound.
    [61] The twelfth of the present invention relates to the urea-urethane composition according to any one of the eighth to eleventh aspects of the present invention, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.
    [62] 13th of this invention, the polyisocyanate compound and the hydroxy compound are made to react on condition that the ratio of the molar number of the polyisocyanate compound / hydroxyl equivalent number of a hydroxy compound becomes 100/1-1/2, and the said polyisocyanate After forming one or more urethane groups from a portion of the isocyanate groups of the compound, an amino compound is added thereto to react the remaining isocyanate groups of the polyisocyanate compound with the amino compound to form one or more urea groups. It relates to a manufacturing method.
    [63] 14th of this invention is made to react the polyisocyanate compound and an amino compound on condition that the ratio of the molar number of the polyisocyanate compound / the amino equivalent number of an amino compound becomes 100/1-1/2, and isocyanate of the said polyisocyanate compound After forming at least one urea group from a portion of the group, a hydroxy compound is added thereto to react the remaining isocyanate groups of the polyisocyanate compound with the hydroxy compound to form at least one urethane group. It is about a method.
    [64] A fifteenth aspect of the present invention is the manufacturing method of the urea-urethane composition according to the thirteenth or fourteenth aspect of the present invention, wherein the reaction for forming at least one urethane group and the reaction for forming at least one urea group are continuously performed. It is about.
    [65] In the sixteenth aspect of the present invention, a polyisocyanate adduct obtained by the reaction of a polyisocyanate compound and a hydroxy compound is reacted so that an equivalent ratio of an amino compound and an isocyanate group / amino group is 2/1 to 1/100, After forming the above urea group, the present invention relates to a method for producing a urea-urethane composition comprising removing an unreacted amino compound.
    [66] 17th of this invention, the polyisocyanate adduct obtained by reaction of a polyisocyanate compound and an amino compound is made to react so that the equivalent ratio of a hydroxy compound and an isocyanate group / hydroxyl group may be 2/1-1/100, A method for preparing a urea-urethane composition comprising forming one or more urethane groups and then removing the unreacted hydroxy compound.
    [67] 18th of this invention is any one of 13th-17th of this invention,
    [68] Reactions that form one or more urethane groups and / or reactions that form one or more urea groups without solvent, or
    [69] A process for producing a urea-urethane composition, characterized in that the reaction of forming at least one urethane group and / or the reaction of forming at least one urea group is carried out using the same solvent.
    [70] The nineteenth aspect of the present invention is the process according to any one of thirteenth to eighteenth aspects of the present invention, wherein the reaction for forming one or more urethane groups and / or the reaction for forming one or more urea groups is performed at a temperature of 0 to 300 ° C. It relates to a method for producing a urea-urethane composition.
    [71] 20th of the present invention is the urea of any one of 13-19 of the present invention, characterized in that the reaction for forming at least one urethane group and / or the reaction for forming at least one urea group is carried out in the presence of a catalyst. It relates to a process for producing a urethane composition.
    [72] The twenty-first aspect of the present invention relates to a color developing composition containing a urea-urethane compound-containing developer.
    [73] A twenty-second aspect of the present invention relates to a color developing composition containing a urea-urethane compound-containing developer and a colorless or light-colored dye precursor.
    [74] Twenty-third of the present invention relates to a color developing composition according to the twenty-second aspect of the present invention, wherein the colorless or light-colored dye precursor is a leuco dye.
    [75] The twenty-fourth aspect of the present invention is the urea-urethane compound according to any one of the twenty-first to twenty-third aspects of the present invention, wherein the developer is the urea-urethane compound according to any one of the first to fourth aspects of the present invention, and the fifth to twelfth aspects of the present invention. A urea-urethane composition according to any one of the above, or a composition prepared by the manufacturing method according to any one of the thirteenth to twentieth aspects of the present invention.
    [76] A twenty-fifth aspect of the present invention is the twenty-third or twenty-fourth aspect of the present invention, wherein the leuco dye is one selected from triarylmethane-based leuco dyes, fluorane-based leuco dyes, fluorene-based leuco dyes, and diphenylmethane-based leuco dyes. It is related with the color development composition characterized by the above leuco dye.
    [77] A twenty-sixth aspect of the present invention relates to a chromophoric composition according to the twenty-third or twenty-fourth aspect of the present invention, wherein the leuco dye is a compound represented by the following Chemical Formula:
    [78]
    [79] [Wherein Y 2 and Y 3 are both an alkyl group or an alkoxyalkyl group,
    [80] Y 4 is a hydrogen atom, an alkyl group or an alkoxy group,
    [81] Y 5 and Y 6 are each a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group].
    [82] A twenty-seventh aspect of the present invention relates to a chromophoric composition according to the twenty-third or twenty-fourth aspect of the present invention, wherein the leuco dye is a compound represented by the following formula:
    [83]
    [84] [Wherein R 5 and R 6 are each a group represented by the following formula k or formula l:
    [85]
    [86] Wherein each of R 11 to R 15 is a hydrogen atom, a halogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 alkoxy group, or each of R 16 and R 17 is an alkyl group having 1 to 8 carbon atoms -NR 16 R 17 }, or
    [87]
    [88] {Wherein, R 18 and R 19 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group};
    [89] Each of R 7 to R 10 is a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or each of R 20 and R 21 is an alkyl group of 1 to 8 carbon atoms -NR 20 R 21 ].
    [90] The twenty-eighth aspect of the present invention relates to a color developing composition according to any one of the twenty-first to twenty-seventh aspects of the present invention, wherein the melting point of the urea-urethane compound developer is 40 ° C or more and 500 ° C or less.
    [91] The twenty-ninth aspect of the present invention is the coloring composition according to any one of the twenty-first to twenty-seventh aspects of the present invention, wherein the urea-urethane compound developer contains a compound selected from compounds represented by the following formulas (V) and (VI). It is about:
    [92]
    [93] [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group. , Isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom, each moiety may have a substituent,
    [94] γ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH- (wherein n is 1 or 2), and The group is selected from the group consisting of any of the groups shown, or does not exist:
    [95] [Formula a]
    [96] ]; And
    [97]
    [98] [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group. May be substituted with an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, and each residue may have one or more substituents,
    [99] δ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C (CF 3 ) 2 -and -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2) or not present.
    [100] 30th of this invention is a coloring composition in any one of the 21st-27th of this invention, Comprising: The said urea-urethane compound developing agent contains the compound chosen from the compound represented by following formula (XX) and (XXI). It is about:
    [101]
    [102] .
    [103] Thirty-first aspect of the present invention relates to a color-forming composition according to any one of claims 21 to 30, further comprising a heat-meltable material.
    [104] In a thirty-second aspect of the present invention, in the thirty-first aspect of the present invention, the heat-soluble material is β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, di-p And at least one compound selected from -methylbenzyl oxalate, 1,2-diphenoxymethylbenzene, m-terphenyl and stearamide.
    [105] Thirty-third aspect of the present invention relates to a color developing composition according to the thirty-first aspect of the present invention, wherein the heat-meltable material is represented by the following general formula (XV):
    [106]
    [107] [Wherein Y is -SO 2 -,-(S) n- , -O-, -CO-, -CH 2- , -CH (C 6 H 5 )-, -C (CH 3 ) 2- , -COCO-, -CO 3 -, -COCH 2 CO-, -COOCH 2 -, -CONH-, -OCH 2 - , and -NH- {wherein, n is 1 or 2} and either one of,
    [108] The hydrogen atom of each benzene ring is a halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanate group, isothiocyanate group, mercapto group, sulfamoyl group, sulfonic acid group, amino group, aromatic compound residue , An aliphatic compound residue or a heterocyclic compound residue.
    [109] Thirty-fourth aspect of the present invention relates to a color developing composition according to the thirty-third aspect of the present invention, wherein the heat-meltable material is represented by the following general formula (XVII):
    [110]
    [111] [Wherein, the hydrogen atom of each benzene ring is a halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanate group, isothiocyanate group, mercapto group, sulfamoyl group, sulfonic acid group, amino group , Aromatic compound residues, aliphatic compound residues or heterocyclic compound residues.
    [112] The thirty-fifth aspect of the present invention further relates to a color developing composition according to any one of the twenty-first to thirty-fourth aspects of the present invention, further comprising an isocyanate compound.
    [113] 36th of this invention is related with the color development composition in any one of 21st-34th of this invention containing an isocyanate compound and an imino compound further.
    [114] The thirty-seventh aspect of the present invention further relates to a color developing composition according to any one of the twenty-first to thirty-sixth aspects of the present invention, further comprising an amino compound.
    [115] Thirty-eighth aspect of the present invention relates to a color developing composition according to any one of the twenty-first to thirty-seventh aspects of the present invention, wherein the developer further contains an acidic developer.
    [116] According to a thirty-third aspect of the present invention, in the thirty-eighth aspect of the present invention, the acidic developer is 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4'-hydroxyphenylsulfone, bis ( One or more selected from 3-allyl-4-hydroxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone and 4,4 '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol It relates to a color developing composition, characterized in that it is a developer.
    [117] 40th of this invention is related with the color development composition in any one of 21st-39th of this invention containing fluorescent dye further.
    [118] The forty-first aspect of the present invention relates to a color developing composition according to any one of the twenty-first to forty-third, which further contains a shelf-stability imparting agent.
    [119] A forty-second aspect of the present invention is a recording material comprising a support and a color developing layer formed on the support.
    [120] The coloring layer is any one of the urea-urethane compound of any one of the first to fourth of the present invention, the urea-urethane composition of any one of the fifth to twelfth of the present invention, or the twenty-first to the fourth of the present invention. It relates to a recording material characterized by containing a coloring composition.
    [121] A forty-third aspect of the present invention relates to a recording material according to a forty-second aspect of the present invention, wherein a protective layer of a color-emitting layer is formed on the color-emitting layer.
    [122] A forty-fourth aspect of the present invention relates to the recording material according to the forty-third aspect of the present invention, wherein the protective layer contains a water-soluble polymer.
    [123] A forty-fifth aspect of the present invention relates to the recording material according to the forty-third or forty-fourth aspect of the present invention, wherein the protective layer contains an inorganic pigment and / or an organic pigment.
    [124] A forty-sixth aspect of the present invention is the recording material according to any one of the forty-third to fifty-seventh aspects of the present invention, wherein the protective layer contains a lubricant.
    [125] A forty-ninth aspect of the present invention relates to a recording material according to a forty-second aspect of the present invention, wherein an intermediate layer is formed on the support, and a color developing layer is formed on the intermediate layer.
    [126] A forty-eighth aspect of the present invention relates to a recording material according to the forty-eighth aspect of the present invention, wherein the intermediate layer contains a water-soluble polymer.
    [127] A forty-ninth aspect of the present invention relates to the recording material according to the forty-ninth or forty-eighth aspect of the present invention, wherein the intermediate layer contains an inorganic pigment and / or an organic pigment.
    [128] A fifty fiftyth aspect of the present invention relates to a recording material according to a forty-second aspect of the present invention, wherein a back coating layer is formed on a support on the side opposite to the surface on which the color development layer is formed.
    [129] A fifty-first aspect of the present invention relates to a recording material according to a fifty aspect of the present invention, wherein the back coating layer contains a water-soluble polymer.
    [130] A fifty-second aspect of the present invention relates to the recording material according to the fifty or fifty-first aspect of the present invention, wherein the back coating layer contains an inorganic pigment and / or an organic pigment.
    [131] The fifty-third aspect of the present invention is the recording material according to any one of the twenty-second to twenty-second aspects of the present invention, wherein as the dispersant for the urea-urethane compound, at least one compound selected from a water-soluble polymer and an anionic surfactant is used. It is about.
    [132] The fifty-fourth aspect of the present invention is the dispersing agent of a urea-urethane compound according to any one of the twenty-second to twenty-second aspects of the present invention, comprising: poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropyl- A recording material characterized by using at least one compound selected from methyl cellulose, condensed sodium naphthalene sulfonate, polycarboxylic acid ammonium salt, water soluble low molecular weight copolymer, and sodium 2-ethylhexylsulfosuccinate.
    [133] A fifty-fifth aspect of the present invention is the use of at least one compound selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant as a dispersant for the dye precursor according to any one of the forty-fourth to fifty-fourth aspect of the present invention. It relates to a recording material.
    [134] 56th of this invention is a dispersing agent of a dye precursor in any one of 42-54 of this invention, methylcellulose, hydroxypropylmethyl cellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate, and sodium A recording material characterized by using at least one compound selected from 2-ethylhexylsulfosuccinate.
    [135] A fifty-seventh aspect of the present invention relates to a recording material according to any one of the forty-second to fifty-eighth embodiments of the present invention, which is a heat-sensitive recording material.
    [136] A fifty-eighth aspect of the present invention relates to a thermal recording material according to a fifty-seventh aspect of the present invention, wherein the average particle size of the urea-urethane compound is 0.05 µm or more and 5 µm or less.
    [137] A fifty-ninth aspect of the present invention relates to a thermal recording material according to a fifty-seventh or fifty-eighth aspect, wherein the liquid temperature at the time of grinding the urea-urethane compound is 60 ° C or less.
    [138] A sixtyth aspect of the present invention relates to a thermal recording material according to any one of the fifty-ninth to thirty-ninth aspects of the present invention, wherein the pH of the urea-urethane compound milling is 5 to 10.
    [139] A fifty sixth aspect of the present invention is the thermally sensitive recording material according to any one of items 57 to 60, wherein at least one compound selected from a water-soluble polymer and an anionic surfactant is used as the dispersant for the heat-fusible material. It is about.
    [140] The sixty-second aspect of the present invention is the dispersing agent of a thermomeltable material according to any one of the fifty-sixth to sixty sixth aspects of the present invention, comprising: poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropylmethyl cellulose And at least one compound selected from condensed sodium naphthalene sulfonate, polycarboxylic acid ammonium salt, water soluble low molecular weight copolymer, and sodium 2-ethylhexylsulfosuccinate.
    [141] A sixty-third aspect of the present invention relates to a thermal recording material according to any one of the fifty-third aspect of the present invention, wherein the urea-urethane compound and the heat-fusible material are finely ground at the same time.
    [142] A sixty-second aspect of the present invention relates to a thermal recording material according to any one of the fifty-third aspect of the present invention, wherein the pH of the support surface coated with the thermal recording layer of the thermal recording material is from 3 to 9. .
    [143] A sixty-fifth aspect of the present invention is directed to the fifty-ninth aspect of the present invention, wherein in order to form a thermal recording layer of the thermal recording material, a thermal coating solution having a pH of 5 to 12 is applied onto the support. A method for producing a thermal recording material.
    [144] A forty-sixth aspect of the present invention relates to the recording material according to the forty-second aspect of the present invention, which is a thermosensitive magnetic recording material.
    [145] In a sixty sixth aspect of the present invention, in the sixty-sixth aspect of the present invention, a thermal recording layer containing a urea-urethane compound developer is formed on one side of the support, and a magnetic recording layer is formed on the other side. A magnetic recording material.
    [146] A sixty-eighth aspect of the present invention relates to a train ticket that is a thermal magnetic recording material according to a sixty-sixth or sixty-seventh aspect of the present invention.
    [147] A sixty-ninth aspect of the present invention relates to a ticket right, which is a thermal magnetic recording material according to the sixty-sixth or sixty-seventh aspect of the present invention.
    [148] A forty-seventh aspect of the present invention relates to a recording material according to the forty-second aspect of the present invention, which is a label for thermal recording.
    [149] The seventy-first aspect of the present invention relates to the label for thermal recording according to claim 70, wherein a recording layer containing a urea-urethane compound developer is formed on one side of the support, and an adhesive layer is formed on the other side.
    [150] A seventy-second aspect of the present invention relates to a label for thermal recording according to the seventy-first aspect of the present invention, wherein a back coating layer is formed between the adhesive layer and the support.
    [151] Seventy-third of the present invention relates to a thermal-sensitive recording label according to the seventy-first or seventy-eighth aspect of the present invention, wherein an intermediate layer is formed between the thermal recording layer and the support.
    [152] A seventy-fourth aspect of the present invention relates to a thermally sensitive label according to any one of the seventy-first to seventy-third aspects of the present invention, wherein a protective layer is formed on the thermally sensitive recording layer.
    [153] A forty-ninth aspect of the present invention relates to a recording material according to a forty-second aspect of the present invention, which is a multicolor thermal recording material.
    [154] 76. The multicolor thermal recording material according to the seventy-seventh aspect of the present invention, wherein two or more thermal recording layers are formed on one side of the support, wherein the recording material is a urea-urethane compound string on one or more of the thermal recording layers. It relates to a multicolored thermosensitive recording material characterized by containing a colorant.
    [155] A seventy-seventh aspect of the present invention relates to the multicolored thermosensitive recording material of the 76th aspect of the present invention, wherein an intermediate layer is formed between the thermally sensitive recording layers.
    [156] A seventy-eighth aspect of the present invention is a multicolor thermosensitive recording material comprising a support and two thermal recording layers laminated on one side of the support,
    [157] One side of the support is formed by laminating a thermal recording layer having a different color development temperature and developing a different color tone, respectively, and the upper thermal recording layer is an agent used as both a color developer and a color developer, or a reversible developer. And a lower thermal recording layer, wherein the lower thermal recording layer contains a urea-urethane compound developer.
    [158] The seventy-ninth aspect of the present invention is the seventy-eighth aspect of the present invention, wherein, in the two thermosensitive recording layers, the upper layer is a low-temperature coloring layer that can develop at low temperatures and discolor at high temperatures, and the lower layer is developed at high temperatures. It relates to a multicolored thermosensitive recording material characterized by being a high temperature coloring layer which can be used.
    [159] An eightyth aspect of the present invention relates to an article for laser marking, characterized by having a thermally sensitive recording layer containing a urea-urethane compound developer on its surface.
    [160] An eighty-eighth aspect of the present invention relates to an article for laser marking, characterized by having a thermally sensitive recording layer containing a colorless or pale dye dye precursor, a urea-urethane compound developer, and a recording sensitivity enhancer.
    [161] 82nd of the present invention is a laser marking for 80th or 81th aspect of this invention which has a protective layer containing the aqueous binder whose glass transition temperature is 20-80 degreeC on the said thermosensitive recording layer. It relates to an article.
    [162] [0218] A thirty eighth aspect of the present invention is the article for laser marking according to the eighty-eighth aspect of the present invention, wherein the recording sensitivity enhancer is at least one compound selected from aluminum hydroxide, muscovite, wollastonite and kaolin. It is about.
    [163] 84th of this invention is an article for laser markings in any one of 80-83 of the present invention, It is any one of labels, packaging materials, and containers.
    [164] 85th of this invention relates to the manufacturing method of the laser marking article characterized by apply | coating the coloring marking composition containing a urea-urethane compound developer on a support body, and drying the support body processed as mentioned above.
    [165] The 86th aspect of this invention is apply | coated to the support body, the coloring marking composition containing a colorless or pale dye dye precursor, a urea-urethane compound developer, and a recording sensitivity improver, and drying the support body processed as mentioned above, It characterized by the above-mentioned. A method for producing an article for laser marking.
    [166] 87. The present invention relates to a method for marking an article characterized by irradiating laser light to the thermal recording layer of the laser marking article according to any one of claims 80 to 84 of the present invention.
    [167] The 88th aspect of this invention is related with the coloring marking composition containing urea-urethane compound developing agent.
    [168] A twenty-ninth aspect of the present invention relates to a coloring marking composition comprising a colorless or pale dye dye precursor, a urea-urethane compound developer, and a recording sensitivity improving agent.
    [169] Best Mode for Carrying Out the Invention
    [170] The present invention is described in detail below.
    [171] Each of the first to fourth urea-urethane compounds of the invention has one or more urea groups and one or more urethane groups.
    [172] In the first to fourth urea-urethane compounds of the present invention, aliphatic compound residues are bonded to terminal oxygen atoms of the urethane group. Thus, the urea-urethane compound can be obtained as a compound having excellent physical and chemical stability, particularly thermal stability. In addition, urea-urethane compounds can be obtained using relatively inexpensive materials.
    [173] In addition, the starting alcohol compound for the aliphatic compound residue bonded to the terminal oxygen atom of the urethane group can be easily removed even if it remains unreacted in the synthesis reaction of the urea-urethane compound. Thus, urea-urethane compounds can be obtained with high purity.
    [174] Preferred forms of both ends of the urea group vary depending on the molecular size of the urea-urethane compound. In the urea-urethane compounds of formula c, each end of the urea group must be bonded to an aromatic compound residue. It is preferable that the said aromatic compound residue is an aromatic ring represented by following General formula (d). In the urea-urethane compounds of formulas e and f, which have a relatively large molecular size, the groups at both ends of the urea group are, for example:
    [175] In formula (e), the groups at both terminals may be any one of an aromatic compound residue, a heterocyclic compound residue, and an alicyclic compound residue,
    [176] In formula f, the groups at both ends may be aromatic compound residues or heterocyclic compound residues. In both formulas e and f, it is preferred that both terminal groups of the urea group are aromatic compound moieties. Urea groups and urethane groups are contiguous through one or more compound moieties (hereinafter such structural moieties are referred to as urea-urethane structural moieties). It is preferred that only one compound residue is present between the urea group and the urethane group. In addition, it is preferable that the said residue is an aromatic ring.
    [177] Although the specific mechanism of the first to fourth urea-urethane compounds of the present invention having a function as a developer is not clear, the function is assumed to be due to the interaction between the urea group and the urethane group in the urea-urethane structure portion. do. The number of urea-urethane structural moieties is at least two in formulas e and f. On the other hand, in some cases in the urea-urethane compound of formula c or d, the number of urea-urethane structural moieties is one. In this case, the following is assumed: In the urea-urethane compound of the formula (c) or d, in order for the compound to function as a developer, to some extent, the residues bonded to both ends of the urea group are the most preferable residues, namely Limited to aromatic compound residues; In the formulas e and f, on the other hand, the residues bonded to both ends of the urethane group need not always be aromatic compound residues.
    [178] The number of urea-urethane structural moieties present in the molecule is 1 to 10, preferably 1 to 5, more preferably 2 to 4 in the molecule.
    [179] The urea-urethane compound may have one or more other urea groups and urethane groups in addition to the urea-urethane structural moiety in the molecule.
    [180] The term "aliphatic" as used in the first to fourth cases of the present invention includes the term "alicyclic".
    [181] The term "aliphatic compound residue" as used in the first to fourth cases of the present invention means a moiety bound by a carbon atom of a portion of the moiety thereof, and the term "aromatic compound moiety" refers to a benzene ring in its moiety. It means a moiety bonded by a carbon atom of an aromatic ring, such as "heterocyclic compound moiety" means a moiety bound by a carbon atom to form a heterocyclic ring in the moiety.
    [182] Further, preferred examples of aliphatic compound residues, heterocyclic compound residues and aromatic compound residues include alkyl groups, cycloalkyl groups, phenyl groups, amide groups, alkoxyl groups, nitro groups, nitrile groups, halogen atoms, formyl groups, di Alkylamino groups, toluenesulfonyl groups and methanesulfonyl groups.
    [183] One that exists in each molecular structure of the first to fourth urea-urethane compounds of the present invention, when it is contemplated that the first to fourth urea-urethane compounds of the present invention are used as a developer or in a thermal recording material. The sum total of the number of the above aliphatic urethane groups and one or more urea groups is 2 or more and 11 or less, Preferably they are 3 or more and 11 or less, More preferably, they are 4 or more and 11 or less. The ratio of urethane groups / urea groups is preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1 and most preferably 1: 1. The molecular weight of the urea-urethane compound is 5000 or less, preferably 2000 or less.
    [184] In the thermal recording material, it is preferable to use a compound having a melting point. The melting point of the first to fourth urea-urethane compounds of the present invention is preferably in the range of 40 ° C to 500 ° C, more preferably 60 ° C to 300 ° C, and most preferably 60 ° C to 250 ° C.
    [185] The method for synthesizing each of the first to fourth urea-urethane compounds of the present invention is not particularly limited. The method of synthesizing a urea urethane compound by making an isocyanate compound react with an alcohol compound and an amine compound is preferable for the ease.
    [186] The method for preparing the urea-urethane compound of the first general formula (c) of the present invention is not limited. The compound can be obtained, for example, by reacting an alcohol compound of formula (m) with an isocyanate compound of formula (n) and an amine compound of formula (o), for example, according to Scheme A 'or B' :
    [187]
    [188] Wherein R is an aliphatic compound residue which may have one or more substituents;
    [189]
    [190] Wherein A 1 is an aromatic compound moiety which may have one or more substituents; And
    [191]
    [192] Wherein A 2 is an aromatic compound moiety which may have one or more substituents;
    [193]
    [194] .
    [195] The method for producing the second urea-urethane compound of formula d of the present invention is not particularly limited. The compound can be obtained, for example, by reacting an alcohol compound of formula m with an isocyanate compound of formula p and an amine compound of formula q, for example according to Scheme C 'or D':
    [196]
    [197] [In formula, the hydrogen atom of a benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group, Amino groups, oxyamino groups, nitroamino groups, hydrazino groups, ureido groups, isocyanate groups, mercapto groups, sulfo groups, or halogen atoms, each moiety may have one or more substituents; And
    [198]
    [199] Wherein the hydrogen atoms of the benzene ring may be substituted with aromatic compound residues, alicyclic compound residues or heterocyclic compound residues, each residue having one or more substituents;
    [200]
    [201] .
    [202] The method for preparing the urea-urethane compound of the third formula e of the present invention is not limited. The compound can be obtained, for example, by reacting the alcohol compound of formula m with an isocyanate compound of formula r and an amine compound of formula s, for example according to Scheme E 'or F' below. :
    [203]
    [204] [Wherein Y is an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each residue may have one or more substituents]; And
    [205]
    [206] [Wherein, α 1 is an aromatic, aliphatic or heterocyclic compound residue having a valence of 2 or more,
    [207] n is an integer of 2 or more,
    [208] Each residue may have one or more substituents;
    [209]
    [210] .
    [211] The method for preparing the urea-urethane compound of the third general formula f of the present invention is not limited. The compound can be obtained, for example, by reacting an amine compound of formula t with an isocyanate compound of formula r and an alcohol compound of formula u, for example, according to Scheme G 'or H' :
    [212]
    [213] [Wherein, Z 1 is an aromatic compound residue or a heterocyclic compound residue, and each residue may have one or more substituents];
    [214]
    [215] [Wherein β 1 is an aliphatic compound residue having two or more valences and may have one or more substituents,
    [216] n is an integer of 2 or more;
    [217]
    [218] .
    [219] The method for preparing the urea-urethane compound of the fourth general formula g of the present invention is not limited. The compound may be obtained, for example, by reacting the alcohol compound of Formula u with the isocyanate compound of Formula p and the amine compound of Formula q, for example, according to Scheme i 'or J' below. :
    [220]
    [221] .
    [222] The method for preparing the urea-urethane compound of the fourth formula h of the present invention is not limited. The compound can be obtained, for example, by reacting an amine compound of formula (XVII) with an isocyanate compound of formula (p) and an alcohol compound of formula (m), for example, according to Scheme K 'or L' :
    [223]
    [224] [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group. , Isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom, each moiety may have one or more substituents,
    [225] γ 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C ( CF 3 ) 2- , -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2), and a group consisting of any group represented by the following formula a The group is selected from or does not exist:
    [226] [Formula a]
    [227] ];
    [228]
    [229] .
    [230] Compounds of formulas m to u that can be used in the synthesis of the urea-urethane compounds of formulas c to h are described in more detail below.
    [231] As the alcohol compound of the formula m, any alcohol compound may be used as long as it has at least one OH group bonded to each carbon atom of the aliphatic compound. Examples of alcohol compounds are described in Solvent Handbook, Kodansha Scientific Co., Ltd., 9th Chain (1989), pp. 327-420 and pp. 772-817]. The alcohol compound is, for example, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, cyclopentanol, tert-amyl alcohol, 2-pentanol, iso Amyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptanol, octanol, 2-ethyl-1-hexanol, capryl alcohol Aliphatic alcohols such as nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol, and the like; for example, allyl alcohol Unsaturated aliphatic alcohols such as 2-methyl-2-propen-1-ol, crotyl alcohol, propargyl alcohol and the like; Aliphatic alcohols to which aromatic compound residues are bound, such as benzyl alcohol, cinnamil alcohol, etc .; Aliphatic alcohols to which heterocyclic compound residues are bound, such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, furfuryl alcohol, and the like; Halogenated aliphatic alcohols such as 2-chloroethanol and 1-chloro-3-hydroxypropane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether , Diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl Ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether Glycol ethers such as dipropylene glycol monoisobutyl ether, dipropylene glycol monophenyl ether and the like; Ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1 Diols such as, 6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol and the like; Aliphatic polyols such as glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, α-methyl glucoside, sorbitol, sucrose and the like; Such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate-derived polyol, epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, amine-modified polyol, glycerin and propylene glycol Polyether polyols, acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, caster oils obtained by adding alone or a mixture of alkylene oxides, such as ethylene oxide and propylene oxide, to a polyhydric alcohol alone or to a mixture Polyols such as induced polyols, polymeric polyols, halogen-containing polyols, phosphorus-containing polyols and the like; N, N-dialkyl ethanolamine, N, N-dialkyl isopropanolamine, N-alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetra Alkanolamines such as kiss (2-hydroxyethyl) ethylenediamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and the like.
    [232] Of the alcohol compounds exemplified above, monoalcohols having one OH group are preferred, and aliphatic alcohols having 10 or less carbon atoms and glycol ethers are more preferred.
    [233] The isocyanate compound of Formula n is not particularly limited as long as it is an aromatic isocyanate in which two or more isocyanate groups are each bonded to a carbon atom.
    [234] The isocyanate compound is, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene Diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 3,3'- Dimethyl-4,4'-diphenylmethane diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenyl Amines and 4,4 ', 4 "-triisocyanato-triphenylamine. As the isocyanate compound of the formula (n), for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT) and toluene Diisocyanate dimers such as diisocyanate dimers; And diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate can also be used. In addition, water-addition product isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adducts of toluene diisocyanate (trade names: Desmodule L and Coronate L); Amine adducts may be used. Also, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171, the contents of which are incorporated herein by reference, at least two isocyanate groups The compound having can be used.
    [235] Among the isocyanate compounds exemplified above, aromatic isocyanates having isocyanate groups bonded to the benzene ring are preferred. p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, Diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione ( Trade Name: Desmodule TT), 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate, 1,3-bis (3-iso More preferred are cyanato-4-methylphenyl) urea and trimethylolpropane adducts of Toluene Diisocyanate (trade names: Desmodule L and Coronate L). A particularly preferred example of the isocyanate compound of formula n is toluene diisocyanate. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferable. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, can be purchased at low prices, and can also be used as isocyanate compounds of the formula (n). Can be.
    [236] As the amine compound of the formula o, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p- Phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-amino Benzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xyldine, 2,4-xyldine, 3,4-xyldine, 2,6-xyldine, 4-aminobenzonitrile , Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α- Naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, acetoacetate anilide , Trimethylphenylammonium bromide, 4,4 ' -Diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4 '-Diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2- Chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, Dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide , p-amino-N-methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarba Barmoyl) , p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) Aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl ] Aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline , 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2 -(N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfone, 2-chloro-5-N -Phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline , 2-phenoxysulfo Nianiline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulphone, bis [4- (p -Aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3 ' -Dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro -4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2 '-Dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4, 4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) Phon, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3 '-Diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-dia Minobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3- Aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl , 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3- Aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-o-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6- Xyldine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro 4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m- Nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, Metol, 2,4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanic acid, meta Nilic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoro Roaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, jade Thilated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diaminostilbene -2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium na Thiocyanate, Tobias acid (Tobias acid), H acid, J acid, phenyl J acid, 1,4-diamino- include anthraquinone, 1,4-diamino-2,3-dichloro anthraquinone is mentioned.
    [237] The aromatic isocyanate compound of the formula p includes 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate and the like. Among these, toluene diisocyanate is preferable and 2,4-toluene diisocyanate is more preferable.
    [238] The aromatic amine compound of the formula q is not particularly limited as long as at least one amino group is directly bonded to at least one carbon atom of the benzene ring. In addition, the hydrogen atoms of the benzene ring are aromatic compound residues, aliphatic compound residues, heterocyclic compound residues, hydroxyl groups, nitro groups, nitrile groups, carbamoyl groups, sulfamoyl groups, carboxyl groups, nitroso groups, oxyamino Groups, nitroamino groups, hydrazino groups, ureido groups, isocyanate groups, mercapto groups, sulfo groups or halogen atoms. The aromatic amine compound of the formula q is, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxy substituted aniline (eg p-aminobenzoic acid), hydroxyl substituted aniline (eg o-aminophenol, m-aminophenol , p-aminophenol and 2-amino-4-chlorophenol), 2,3-xyldine, 2,4-xyldine, 3,4-xyldine, 2,6-xyldine, nitrile substituted aniline (e.g., 4-aminobenzonitrile), anthranilic acid, p-cresidine, halogen substituted aniline (eg, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, o-chloroaniline, m-chloroaniline and p-chloroaniline), α-naphthylamine, aminoanthracene, o-ethylaniline, methyl p-aminobenzo Ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o- Aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino-4- Methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, carbamoyl aniline (e.g. p- (N-phenylcarbamoyl) aniline, p- [N- ( 4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) -aniline, 2-methoxy -5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline and 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline), 5- Acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 2- Methoxy-4- (N-benzoylamino) -5-methylaniline, sulfamoylaniline (eg, 4-sulfamoylaniline, 3-sulfamoylaniline, 2-chloro-5-N-phenylsulfamoylaniline, 2-meth) Methoxy-5-N, N-diethylsulfamoylaniline and 2,5-dimethoxy-4-N-phenylsulfamoylaniline), 2- (N-ethyl-N-phenylaminosulfonylaniline, 4-dimethylamino Sulfonylaniline, 4-diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfone, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chloro Phenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, nitro substituted aniline (e.g. o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4 -Nitroaniline, 5-chloro-2-nitroaniline, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine and 2-amino-5 -Nitrobenzonitrile), sulfanic acid, methanylic acid, 4B Acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, aromatic monoamines such as m-aminobenzotrifluoride and 2-amino-3-bromo-5-nitrobenzonitrile; Aromatic monoamines having one or more substituents including carboxyl groups, nitroso groups, oxyamino groups, nitroamino groups, hydrazino groups, ureido groups, isocyanate groups, mercapto groups, sulfo groups and the like; And 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'- Dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis [4- (m-aminophenoxy) Phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4 ' -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2, 2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4 '-Diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl Le, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenylmethane, bis (3- Amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldi Benzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2'-bis (4-aminophenoxyphenyl) propane, 4,4'-bis Aromatic diamines such as (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine and the like. Among them, the aromatic monoamine is preferable to be used, and aniline or aniline derivatives are more preferable.
    [239] The isocyanate compound of the formula r is not particularly limited as long as two or more isocyanate groups are each bonded to a carbon atom.
    [240] The compound is, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate Isocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl-carbazole -3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thio Phosphate, 4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine di Isocyanates, Dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl-isocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate.
    [241] As an isocyanate compound of the formula r, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT), toluene diisocyanate dimer and the like Diisocyanate dimers; Diisocyanate trimers such as diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate can also be used. In addition, water-addition product isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adducts of toluene diisocyanate (trade names: Desmodule L and Coronate L); Amine adducts may be used. Also, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171, the contents of which are incorporated herein by reference, at least two isocyanate groups The compound having can be used.
    [242] Among the isocyanate compounds exemplified above, aromatic isocyanates having isocyanate groups bonded to the benzene ring are preferred. p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, di Phenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name) : Desmodule TT), 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate, 1,3-bis (3-isocy More preferred are anato-4-methylphenyl) urea and trimethylolpropane adducts of Toluene Diisocyanate (trade names: Desmodule L and Coronate L). Particularly preferred examples of the isocyanate compound of the formula r are toluene diisocyanate. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferred. In addition to 2,4-toluene diisocyanate, a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate is generally commercially available, It can be purchased at a low price and can also be used as the isocyanate compound of the formula r.
    [243] The amine compound of the formula s is not particularly limited as long as it has two or more amino groups. The compound is, for example, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether , 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis [4- ( m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dime Methoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-di Methoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diamino Biphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3,4'-dia Minodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl Sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-dia Mino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) Propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylene Aromatic amines such as diamine; Guanamine, acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diamino Heterocyclic compound amines such as pyridine, 2,3,5-triaminopyridine and bis (aminopropyl) piperazine; Methanediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,3-diamino-2-hydroxypropane, ethylenediamine, diethylenetriamine, triethylene Tetramine, tetraethylenepentamine, N-methyl-3,3'-iminobis (propylamine), hexamethylenediamine, bis (aminomethyl) cyclohexane, isophoronediamine, isopropylidenebis (aminocyclohexane), And aliphatic amines such as 4,4'-diaminodicyclohexylmethane and xylylenediamine. Among the amine compounds exemplified above, aromatic amines are preferred, with aniline derivatives having two or more amino groups and represented by the formula:
    [244]
    [245] [Wherein, R 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group,
    [246] X 1 and X 2 are independently amino groups or represented by the formula b:
    [247] ;
    [248] Y 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C ( CF 3 ) 2- , -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2), and a group consisting of any group represented by the following formula a The group is selected from or does not exist:
    [249] [Formula a]
    [250] ].
    [251] The amine compounds of formula t are, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-phenyl Rendiamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid , o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xylidine, 2,6-xyldine, 4-aminobenzonitrile, Anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naph Tylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N, N- Diglycidylaniline, N, N-diglycidyl-o-toluidine, acetoacetic acid anyl De, trimethylphenyl ammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether , 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenyl Rendiamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p- Aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4- Cle Lovenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy- 5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2 , 5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methyl Aniline, 4-Sulfamoylaniline, 3-Sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfatiazole , 4-aminodiphenyl sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenyl Sulfamoylaniline, 2 -Methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m -Aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethok Cibiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobi Phenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2 ' -Dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl ether , 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diamino Diphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone , 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino- 2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4 -Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3, 3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-o-toluidine, 4,4'-(p -Phenyleneisopropylidene) -bis- (2,6-xyldine), o-chloro-p-nitroa Aniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, Metol, 2,4-diaminophenol, N- (β- Hydroxyethyl) -o-aminophenol sulfate, sulfanic acid, methacrylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2 , 4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5- Nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3 , 3'-dichlorobenzidine, 4,4'-diaminostilbene-2,2'-disulfonic acid, benzyl Tianiline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2 Aromatic amines such as, 3-dichloroanthraquinone and the like; And 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6 -[2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino Heterocyclic compound amines such as 4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and the like. Among these, aromatic monoamines are preferably used.
    [252] The alcohol compound of the formula u is not particularly limited as long as it is a polyol compound having two or more OH groups. The alcohol compound is ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5- Diols such as pentanediol, 1,6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol and the like; Aliphatic polyols such as glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, α-methyl glucoside, sorbitol, sucrose and the like; Such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate-derived polyol, epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, amine-modified polyol, glycerin and propylene glycol Polyether polyols, acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, caster oils obtained by adding alone or a mixture of alkylene oxides, such as ethylene oxide and propylene oxide, to a polyhydric alcohol alone or to a mixture Polyols such as induced polyols, polymeric polyols, halogen-containing polyols, phosphorus-containing polyols and the like; And N-alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N' Alkanolamines such as N'-tetrakis (2-hydroxypropyl) ethylenediamine and the like. Among them, diols, aliphatic polyols, alkanolamines, and polyols having a molecular weight of 2000 or less are preferably used.
    [253] The amine compound of formula (XVII) is, for example, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, dia Minodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3, 3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5, 5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2 '-Diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl , 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-di Thiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3, 4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'- Diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4, 4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-amino Aromatic diamines such as phenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine and the like. Preferred are amine compounds of the general formula (X ') in which γ 1 is a sulfonyl group or a methylene group.
    [254] In order to obtain each of the first to fourth urea-urethane compounds of the present invention, the isocyanate and the corresponding reactant are mixed in an organic solvent or without a solvent, reacted, and then subjected to filtration, crystallization, desolvation, and the like to determine the crystals. Is collected to obtain the desired compound. The reaction can be carried out by using an excess of a substance having two or more groups in the molecule, and adding a small amount of another substance to be reacted thereto. When the method is employed, it is possible to react only one of two or more groups. It is also desirable to stir the system thoroughly so that the added material is sufficiently dispersed immediately after addition. The above applies to any of the urea-urethane compounds exemplified herein. The reaction method is not limited to the above method, and any method may be employed as long as the same result as described above can be obtained. Each of the above reactants may be used alone or in plurality, depending on the purpose. As the solvent, any solvent can be used as long as it does not react with the isocyanate group and the functional group of the reactant. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons and ketones. Particular preference is given to methyl ethyl ketone, toluene and the like, in which the isocyanate is dissolved and the solubility of the reaction product is low. The reaction product obtained by the above reaction operation is not always a single compound, and in some cases, is obtained as a mixture of compounds having different positions of substituents.
    [255] Specific examples of the first to fourth urea-urethane compounds of the present invention are the following compounds ((S-1) to (S-70)).
    [256]
    [257]
    [258]
    [259]
    [260]
    [261] Each of the urea-urethane compositions according to the fifth to twelfth of the present invention, and the urea-urethane compositions prepared by the thirteenth to twentieth manufacturing methods of the present invention, comprise at least one urethane group (-NHCOO- group) and A urea-urethane compound having at least one urea group (—NHCONH- group) in total of 2 to 10, and having a molecular weight of 5000 or less, preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably It contains at least 70% by weight.
    [262] In order to obtain a color developing composition for a thermal recording material or a pressure-sensitive recording material, the urea-urethane composition may be used in combination with a colorless or pale dye precursor. The color development composition is very effective and has both excellent color development and print retention.
    [263] The urea-urethane compound, which is the main component of the urea-urethane composition, has at least one urea group and at least one urethane group in the molecule. Preferably, the urea group and urethane group are adjacent to each other via one or more compound moieties (hereinafter, such structural moieties are referred to as urea-urethane structural moieties). 10 or less, Preferably they are 3 or more and 10 or less, More preferably, they are 4 or more and 10 or less.
    [264] The ratio of the urethane group / urea group in the molecule of the urea-urethane compound is preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1, most preferably 1: 1. The molecular weight of the urea-urethane compound is 5000 or less, preferably 2000 or less.
    [265] The content of the urea-urethane compound in each of the urea-urethane compositions according to the fifth to twenty of the present invention is at least 50% by weight. The urea-urethane composition may be prepared by a relatively simple manufacturing method. On the other hand, since the ratio of the urea-urethane compound which can exhibit the outstanding coloring ability and storage ability required for a coloring composition is high, it can exhibit the outstanding performance characteristic.
    [266] In addition, as the urea-urethane compound, either a single compound or a mixture of two or more compounds including an isomer may be used.
    [267] In addition, a mixture of two or more compounds including isomers may be used as the urea-urethane compound to improve the color developing ability, the preservation ability, and the like.
    [268] On the other hand, the urea-urethane compound of the present invention may be appropriately diluted with a substance that does not inhibit the effects of the present invention. Such diluents include, for example, heat-meltable materials, acidic developers, amine compounds, isocyanate compounds, urea compounds, urethane compounds, and the like, which are described below. Among them, urea compounds and urethane compounds having a structure similar to urea-urethane compounds are preferred because they can improve the sensitivity. Also preferred are compounds obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound. It is preferable that the said diluent is contained in the obtained dilution liquid in the ratio of 0.0001-50 weight% with respect to the total amount of a urea-urethane compound and a diluent. In order to achieve the storage capacity, the content of the diluent is more preferably 40% by weight or less, even more preferably 30% by weight or less. In order to improve the sensitivity, the content of the diluent is more preferably 0.01% by weight or more, even more preferably 1% by weight or more. In some cases, a diluent is produced during the synthesis reaction of the urea-urethane compound. When a diluent is added, it is preferable to add it during the synthesis reaction in order to improve the sensitivity. For example, a urea-urethane composition having from 2 to 10 in total of at least one urea group and at least one urethane group in a molecular structure and containing a molecular weight of 5000 or less, and a diluent, wherein the diluent is 0.0001 to Preference is given to urea-urethane compositions which contain 50% by weight. Also in the case of the eighth to twelfth compositions of the present invention and the composition prepared by the thirteenth to twentieth manufacturing methods of the present invention, the same effects are observed.
    [269] Each of the urea-urethane compositions according to the fifth to twentieth aspects of the present invention is preferably a colorless or pale solid having a melting point from the viewpoint of its usefulness in the thermal recording material. Melting | fusing point of the said composition becomes like this. Preferably it is 40 degreeC-300 degreeC, More preferably, it is 60 degreeC-260 degreeC.
    [270] A process for the preparation of any of the urea-urethane compositions according to the fifth to twentieth aspect of the invention, wherein at least one urethane group is formed from at least one isocyanate group of the polyisocyanate compound and a hydroxyl group of the hydroxy compound, and then A method of forming at least one urea group from an unreacted isocyanate group of the same polyisocyanate compound and an amino group of the amino compound; or
    [271] Forming at least one urea group from at least one isocyanate group of the polyisocyanate compound and an amino group of the amino compound, followed by forming at least one urethane group from the unreacted isocyanate group of the same polyisocyanate compound and the hydroxyl group of the hydroxy compound The method is preferably employed.
    [272] In the case where at least one urethane group is formed from the polyisocyanate compound and the hydroxy compound, the urea-urethane composition described above uses the polyisocyanate compound in an excessive amount with respect to the hydroxyl group, and the polyisocyanate compound is used with respect to the hydroxy compound. In the amount of one molecule per hydroxyl group of to react only one isocyanate group of the polyisocyanate compound, leaving at least one isocyanate group unreacted, and then reacting the remaining unreacted isocyanate group with an amino compound. It can be obtained efficiently by forming one or more urea groups.
    [273] In this case, the polyisocyanate compound and the hydroxy compound are subjected to the conditions under which the ratio of the molar number of the polyisocyanate compound to the hydroxyl equivalent number of the hydroxy compound is 100/1 to 1/2, and the isocyanate group equivalent of the polyisocyanate compound. It is preferred to react under conditions such that the ratio of the hydroxyl equivalent number of the water / hydroxy compound is from 1000/1 to 1/1 to form one or more urethane groups.
    [274] When adding a hydroxy compound to the polyisocyanate compound, it is preferable to add a small amount of the hydroxy compound in the reaction system so that the polyisocyanate compound is always present in an excessive amount relative to the hydroxyl group. The addition method is particularly preferred when the reaction is carried out such that the ratio of the molar number of polyisocyanate compounds / hydroxyl equivalent number of hydroxy compounds is about 1/1, for example 5/1 to 1/2.
    [275] Similarly, when at least one urea group is formed from a polyisocyanate compound and an amino compound, the urea-urethane composition may use the polyisocyanate compound in excess with respect to the amino group and the polyisocyanate compound with respect to the amino compound, By binding one molecule per amino group to react one isocyanate group of the polyisocyanate compound, leaving at least one isocyanate group unreacted, and then reacting the remaining unreacted isocyanate group with the hydroxy compound, It can be obtained efficiently by forming one or more urethane groups. In this case, the polyisocyanate compound and the amino compound are subjected to the conditions under which the ratio of the molar number of the polyisocyanate compound / amino equivalent number of the amino compound is 100/1 to 1/2, and the isocyanate group equivalent number / amino of the polyisocyanate compound. It is preferred to react under conditions such that the ratio of the number of amino equivalents of the compound is from 1000/1 to 1/1 to form one or more urea groups.
    [276] When adding an amino compound to the polyisocyanate compound, it is preferable to add a small amount of the amino compound in the reaction system so that the polyisocyanate compound is always present in an excessive amount relative to the amino group. The addition method is particularly preferred when the reaction is carried out such that the ratio of the molar number of polyisocyanate compounds / amino equivalent number of amino compounds is approximately 1/1, for example 5/1 to 1/2.
    [277] In the process for the preparation of any of the urea-urethane compositions according to the fifth to twenty of the present invention, the reaction of the polyisocyanate compound with the hydroxy compound to form at least one urethane group is carried out without solvent, or without solvent solvent. Hydroxy compound, a dilution of a solvent and a hydroxy compound, or a hydroxy compound dispersion in a solvent, is continuously, or partly added, dropwise or injected into a dilution of a solvent and a polyisocyanate compound or a dispersion of a polyisocyanate compound in a solvent. It is preferable. Similarly, the reaction of an amino compound with a polyisocyanate compound to form one or more urea groups is carried out without solvent, or a solvent-free amino compound, a dilution of a solvent and an amino compound, or an amino compound dispersion in a solvent, a solvent and a polyisocyanate compound. It can be carried out by adding, dropping or injecting continuously or in part to a dilution solution of the polyisocyanate compound or a dispersion of the polyisocyanate compound in a solvent.
    [278] The production method comprising adding a hydroxy compound or an amino compound in small amounts to the polyisocyanate compound, in particular, in the reaction method for preparing the urea-urethane composition, while at least one isocyanate group remains in the molecule of the polyisocyanate compound, Preference is given when other isocyanate groups are reacted with hydroxy compounds or amino compounds to form one or more urethane groups or urea groups, respectively. In addition, the above production method is preferable when a hydroxy compound having two or more hydroxyl groups or an amino compound having two or more amino groups is reacted with a polyisocyanate compound having two or more isocyanate groups.
    [279] In carrying out the reaction, it is preferred that the system is thoroughly stirred so that the hydroxy or amino compound added, dropped or injected into the polycyanate is immediately and sufficiently dispersed. For example, it is preferable to thoroughly stir the reaction system by adjusting the stirring speed in the reactor, selecting a stirring blade, or installing a baffle plate.
    [280] The reaction to form at least one urethane group and the reaction to form at least one urea group are preferably carried out individually and sequentially. If they are carried out simultaneously, the urea-urethane content of the urea-urethane composition is lowered, which is undesirable. The urethane group formation reaction and urea group formation reaction are preferably carried out continuously. In the process of the present invention, since the separation and purification process during the production is not necessary, the production can be simplified by carrying out two reaction processes successively.
    [281] In the preparation of any of the urea-urethane compositions according to the fifth to twenty of the present invention, when a polyisocyanate adduct with a hydroxy compound is used, which is an isocyanate already having at least one urethane group in the molecule, said urea-urethane The composition can be obtained by reacting the adduct with an amino compound. In this case, it is preferred to carry out the reaction at an equivalent ratio of isocyanate groups / amino groups of 2/1 to 1/100 to form at least one urea group and to remove the unreacted amino compound.
    [282] In the preparation of any of the urea-urethane compositions according to the fifth to twenty of the invention, when a polyisocyanate adduct with an amino compound is used, which is an isocyanate which already has at least one urea group in the molecule, said urea-urethane composition Can be obtained by reacting the adduct with a hydroxy compound. In this case, it is preferred to carry out the reaction at an equivalent ratio of isocyanate groups / hydroxyl groups of 2/1 to 1/100 to form at least one urethane group and to remove the unreacted hydroxy compound.
    [283] In the preparation of any of the urea-urethane compositions according to the fifth to twenty of the present invention, when a solvent is used to carry out the reaction (s), the solvent is not particularly limited as long as it does not react with isocyanate groups or the like. Do not. Such solvents include, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons, ketones and phosphate esters. Especially preferred are acetone, methyl ethyl ketone, toluene and the like, in which isocyanate is dissolved and the solubility of the reaction product is low. If high solubility is required for isocyanates, phosphate esters, in particular trimethyl phosphate, are preferred.
    [284] When using such a solvent, in order to facilitate the reuse of the solvent and the continuous performance of the urea group formation reaction and the urethane group formation reaction, it is preferable that the at least one urethane group formation and the at least one urea group formation are performed in the same single solvent. desirable.
    [285] The reaction temperature at which the polyisocyanate reacts with the hydroxy compound and / or the amino compound to form at least one urethane group and / or at least one urea group is from 0 ° C to 300 ° C, preferably from 5 ° C to 200 ° C, more preferably 10 ℃ to 150 ℃. The reaction temperature is appropriately adjusted depending on the polyisocyanate compound, hydroxy compound and amino compound selected. It is also possible to carry out urethane group formation and urea group formation at appropriate different temperatures, respectively.
    [286] Catalysts may be used to react the polyisocyanate with hydroxy compounds and / or amino compounds to form one or more urethane groups and / or one or more urea groups. The catalyst may be, for example, a quaternary amine compound such as triethylamine, 1,4-diazabicyclo (2,2,2) octane, or the like; Organic acid tin salts such as dibutyltin dilaurate and the like. Usually, the catalyst concentration is 1 to 10,000 ppm, preferably 10 to 2,000 ppm, relative to the isocyanate compound. Among the catalysts exemplified above, quaternary amine compounds are preferred.
    [287] A urea-urethane composition containing a urea-urethane compound having a plurality of urea-urethane structural moieties in a molecule may be prepared by the process of the production method of the present invention, for example, an amino compound having two or more amino groups and two or more hydroxyl groups. Using a hydroxy compound having, it can be obtained by repeating two or more times. Since sufficiently high yields of reactions can be achieved in each process, the production process of the present invention allows relatively easy preparation of urea-urethane compositions having high performance characteristics.
    [288] The polyisocyanate compound used in each of the fifth to twentieth of the present invention is not particularly limited as long as it has at least two isocyanate groups each bonded to a carbon atom. The polyisocyanate compound is, for example, p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4- Toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl- Carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate ) Thiophosphate, 4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanatotriphenylamine, m-xylylene diisocyanate, Lee Diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl-comprises a diisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate. As polyisocyanate compounds, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT) and toluene diisocyanate divalent Diisocyanate dimers such as sieves; And diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate can also be used. In addition, water-addition product isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adducts of toluene diisocyanate (trade names: Desmodule L and Coronate L); And amine adducts may be used. Also, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171, the contents of which are incorporated herein by reference, at least two isocyanate groups The compound having can be used.
    [289] Among the compounds exemplified above, preferred examples of the polyisocyanate compounds include aromatic polyisocyanates having isocyanate groups bonded to a benzene ring, such as p-phenylene diisocyanate, m-phenylene diisocyanate, o-phenylene diisocyanate, 2 , 4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, triphenylmethane triisocyanate, N , N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT), 4,4', 4 "-trimethyl-3,3 ', 3 Trimethylolpropane adduct of "-triisocyanato-2,4,6-triphenylcyanurate, 1,3-bis (3-isocyanato-4-methylphenyl) urea, and toluene diisocyanate Desmodule L and Corona te L) and the like. Particularly preferred examples of the polyisocyanate compound are toluene diisocyanate. Among these toluene diisocyanates, 2,4-toluene diisocyanate is preferable. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, can be purchased at low prices, and can also be used as polyisocyanate compounds.
    [290] As hydroxy compounds which react with polyisocyanate compounds to form one or more urethane groups, phenolic compounds and alcohol compounds are mentioned.
    [291] The phenolic compound is, for example, phenol, cresol, xenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclo Hexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane, 2, 2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, Pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis ( 4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone Phon, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-isopropylphenyl -4'-hydroxyphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'- Dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-di Hydroxy-diphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2,4 -Dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylynilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4 '-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate ), Hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (benzyl Oxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxy Salicylic acid, 4-n-octyloxy-carbonylaminosalicylic acid and 4-n-octanoyloxy-carbonylaminosalicylic acid.
    [292] Among the phenolic compounds exemplified above, a phenol derivative represented by the following formula (w) and a diphenol compound represented by the following formula (XVI) are preferable.
    [293]
    [294] [In formula, the hydrogen atom of a benzene ring is an alkyl group, a cycloalkyl group, a phenyl group, an amide group, an alkoxyl group, a nitro group, a nitrile group, a halogen atom, a formyl group, a dialkylamino group, a toluenesulfonyl group, May be substituted with a methanesulfonyl group or an OH group; And
    [295]
    [296] [In formula, it is preferable that the hydrogen atom of each benzene ring is substituted by the substituent which is an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. However, the said substituent is a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group. , Sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom, The residue may have one or more substituents,
    [297] δ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C (CF 3 ) or a group selected from the group consisting of 2 -and -CR 2 R 3 -wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2;
    [298] The term "aliphatic" used in the fifth to twentieth cases of the present invention includes the term "alicyclic".
    [299] The term "aliphatic compound residue" as used in the fifth to twentieth cases of the present invention means a residue bound by a carbon atom of the aliphatic hydrocarbon portion of the residue. The term "aromatic compound residue" as used herein. Means a residue bonded by a carbon atom of an aromatic ring such as a benzene ring of a residue. The term "heterocyclic compound residue" as used herein means a residue bound by a carbon atom to form a heterocyclic ring of residues.
    [300] Preferred examples of the substituents of aliphatic compound residues, heterocyclic compound residues and aromatic compound residues are alkyl groups, cycloalkyl groups, phenyl groups, amide groups, alkoxyl groups, nitro groups, nitrile groups, halogen atoms, formyl groups, di Alkylamino groups, toluenesulfonyl groups and methanesulfonyl groups.
    [301] As alcohol compounds, mention is made of compounds having at least one OH group bonded to a carbon atom of an aliphatic compound. Examples of alcohol compounds are described in Solvent Handbook, Kodansha Scientific Co., Ltd., 9th Chain (1989), pp. 327-420 and pp. 772-817]. The alcohol compound is, for example, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, pentanol, cyclopentanol, tert-amyl alcohol, 2-pentanol, iso Amyl alcohol, hexanol, 3-hexanol, cyclohexanol, cyclohexylmethanol, 4-methyl-2-pentanol, heptanol, isoheptanol, octanol, 2-ethyl-1-hexanol, capryl alcohol Aliphatic alcohols such as nonyl alcohol, isononyl alcohol, decanol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isostearyl alcohol and the like; Unsaturated aliphatic alcohols such as allyl alcohol, 2-methyl-2-propen-1-ol, crotyl alcohol, propargyl alcohol and the like; Aliphatic alcohols to which aromatic compound residues are bound, such as benzyl alcohol, cinnamil alcohol, etc .; Aliphatic alcohols to which heterocyclic compound residues are bound, such as 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, furfuryl alcohol, and the like; Halogenated aliphatic alcohols such as 2-chloroethanol and 1-chloro-3-hydroxypropane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monohexyl ether , Diethylene glycol monophenyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl Ether, propylene glycol monoisobutyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether Glycol ethers such as dipropylene glycol monoisobutyl ether, dipropylene glycol monophenyl ether and the like; Ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1 Diols such as, 6-hexanediol, hexylene glycol, 1,9-nonanediol, neopentyl glycol, methylpentanediol and the like; Aliphatic polyols such as glycerin, castor oil, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, α-methyl glucoside, sorbitol, sucrose and the like; Such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, adipate-derived polyol, epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, amine-modified polyol, glycerin and propylene glycol Polyether polyols, acrylic polyols, fluorinated polyols, polybutadiene polyols, polyhydroxy polyols, caster oils obtained by adding alone or a mixture of alkylene oxides, such as ethylene oxide and propylene oxide, to a polyhydric alcohol alone or to a mixture Polyols such as induced polyols, polymeric polyols, halogen-containing polyols, phosphorus-containing polyols and the like; N, N-dialkyl ethanolamine, N, N-dialkyl isopropanolamine, N-alkyldiethanolamine, N-alkyldiisopropanolamine, triethanolamine, triisopropanolamine, N, N, N ', N'-tetra Alkanolamines such as kiss (2-hydroxyethyl) ethylenediamine, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine and the like.
    [302] Among the alcohol compounds exemplified above, aliphatic alcohols having 10 or less carbon atoms, glycol ethers, diols, aliphatic polyols, polyols having a molecular weight of 2000 or less, and alkanolamines are preferable.
    [303] The alcohol compounds exemplified above may be used alone or in combination, and the phenolic compounds exemplified above may also be used alone or in combination.
    [304] As the amino compound which reacts with the polyisocyanate compound to form at least one urea group, any compound can be used as long as it has at least one amino group each bonded to a carbon atom. The amino compound is, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-phenylenediamine , N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o -Aminophenol, m-aminophenol, p-aminophenol, 2,3-xylidine, 2,4-xylidine, 3,4-xyldine, 2,6-xyldine, 4-aminobenzonitrile, anthranilic acid , p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine , Aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N, N-digly Cydylaniline, N, N-diglycidyl-o-toluidine, acetoacetic acid anilide, Trimethylphenyl ammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3 , 3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine, m-phenylenediamine , p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzo Acetate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o- Aminobenzamide, p-aminobenzamide, p-amino-N-methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chloro Benzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2 -Methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5 -[N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2, 5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfa Moylaniline, 2-meth Ci-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, bis [4- (m-amino Phenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4 , 4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl , 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl -4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl ether, 3 , 3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodi Nilmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2 , 2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4- Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) propane, 4 , 4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4,4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis-o-toluidine, 4,4'-(p- Phenyleneisopropylidene) -bis- (2,6-xyldine), o-chloro-p-nitroaniline , o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p -Nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, Metol, 2,4-diaminophenol, N- (β-hydrate Oxyethyl) -o-aminophenol sulfate, sulfanic acid, methacrylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2, 4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitro Benzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl-p-phenylenediamine, dianisidine, 3, 3'-dichlorobenzidine, 4,4'-diaminostilben-2,2'-disulfonic acid, benzylethyl Aniline, 1,8-naphthalenediamine, sodium naphthionate, tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino-anthraquinone, 1,4-diamino-2, Aromatic amines such as 3-dichloroanthraquinone and the like; And 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6 -[2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino Heterocyclic compound amines such as 4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and the like; And methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhex Siloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine , Propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclo Hexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3 -Amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine It includes aliphatic amines, such as.
    [305] Among the amino compounds exemplified above, aromatic amines are preferred, with aniline derivatives having one or more amino groups and represented by the formula z or VII below:
    [306]
    [307] [Wherein, R 1 and R 2 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group]; or
    [308] [Formula Ⅷ]
    [309]
    [310] [Wherein, R 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group,
    [311] X 1 and X 2 are independently amino groups or represented by the formula b:
    [312] [Formula b]
    [313] ;
    [314] Y 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C ( CF 3 ) 2- , -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2), and a group consisting of any group represented by the following formula a The group is selected from or does not exist:
    [315] [Formula a]
    [316] ].
    [317] The amine compounds may be used alone or in combination.
    [318] The urea-urethane compounds used as the developer in each of the twenty-first and twenty-second aspects of the present invention include compounds having at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) in the molecule. It is called.
    [319] Compounds having at least one urea group are known to have a chromogenic effect, but they are not practical because of low chromogenic concentrations and insufficient storage stability. It is an excellent developer for colorless or pale dye precursors, and a color developing composition containing a urea-urethane compound and a dye precursor, and a recording material obtained using the color developing composition has a high color development concentration and excellent storage stability.
    [320] The mechanism by which the urea-urethane compound exerts an excellent coloring effect is not clear, but the effect is presumed to be due to the interaction between the urea group and the urethane group in the molecule.
    [321] A urea-urethane compound used as a developer in each of the twenty-first and twenty-second aspects of the present invention, wherein the compound has both at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) in the molecule As long as any compound can be used. The urea-urethane compound is an aromatic compound or a heterocyclic compound. In addition, the urea-urethane compound is preferably a compound in which an aromatic compound residue or a heterocyclic compound residue is directly bonded to each terminal of each of the urea group and the urethane group. In the molecule, in addition to the urea group (-NHCONH- group) and urethane group (-NHCOO- group), at least one sulfonic acid group (-SO 2 -group), amide group (-NHCO- group) or isopropylidene group (-C More preferably, the (CH 3 ) 2 -group) is present without being directly bonded to the urea group.
    [322] The molecular weight of the urea-urethane compound is preferably 5000 or less, more preferably 2000 or less. The sum total of the number of urea groups and urethane groups in a urea-urethane compound becomes like this. Preferably it is 20 or less, More preferably, it is 10 or less. The ratio of urea groups / urethane groups in the molecular structure of the urea-urethane compound is preferably 1: 3 to 3: 1, in particular 1: 2 to 2: 1.
    [323] When used in a thermal recording material, the urea-urethane compound is preferably a compound having a melting point. The melting point is preferably 40 ° C to 500 ° C, in particular 60 ° C to 300 ° C.
    [324] In each of the twenty-first and twenty-second aspects of the present invention, a method for synthesizing a urea-urethane compound used as a developer, wherein at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) are formed It is not particularly limited. The method for producing an urea-urethane compound by reacting an isocyanate compound with an OH group-containing compound and an amine compound is preferable because of its ease.
    [325] Specifically, in the case of urea-urethane compounds used as the developer of the present invention, isocyanates having two or more isocyanate groups are used as starting materials, and all isocyanate groups, except at least one isocyanate group, are reacted with the OH group-containing compound so that at least one Urethane groups are formed, and then one or more urea groups may be formed by reaction of the remaining isocyanate groups with the amine compound. In addition, except for at least one isocyanate group, the entire isocyanate group may first be reacted with an amine compound to form one or more urea groups, and then one or more urethane groups may be formed by reaction of the remaining isocyanate group with the OH group containing compound.
    [326] Starting isocyanates are not particularly limited as long as they have two or more isocyanate groups. Starting isocyanates are, for example, p-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane di Isocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl-carbazole-3,6-diisocyanate, 3,3'-dimethyl -4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanato) thiophosphate, 4,4 ', 4 "-triy Socyanato-2,5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene Switch-4-cyclohexyl-comprises a diisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate. As starting isocyanates, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT) and toluene diisocyanate dimer Diisocyanate dimers such as; And diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate can also be used. In addition, water-addition product isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Desmodule L) and; Amine adducts may be used. Further, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-8-225445 and the specification of JP-A-8-250623, compounds having two or more isocyanate groups can be used.
    [327] Particularly preferred examples of such starting isocyanates are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferable. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, can be purchased at low prices, and can also be used as starting isocyanates.
    [328] As the amine compound which reacts with the starting isocyanate to the urea-urethane compound which is a developer, to form at least one urea group, any compound can be used as long as it has at least one amino group. The amine compound is, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N- Diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethine Oxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xyldine, 2,4-xyldine, 3,4-xyldine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N -Propyl aniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-tol Idine, acetoacetic acid anilide, trimethylphenyl ammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, dia Minodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, Isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m- Aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino-4-meth Sibenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4 -Aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbine Barmoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N- Methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4- Diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2, 5-dime Cy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl 4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulphone, bis [4- (p-aminophenoxy) phenyl] sulphone, bis [3-methyl-4- (p-aminophenoxy ) Phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4 '-Diamino-5,5'-dimethoxybiphenyl, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-dia Minobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodi Aniline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-dia Minodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl Sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'- Ethylenedianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-amino Phenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2 -Bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4 , 4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis -o-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6- Ilidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, Metol, 2, 4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanic acid, methacrylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl- p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diami Nostilbene-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-dia Aromatic amines such as mino-anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone and the like; And 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6 -[2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino Heterocyclic compound amines such as 4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and the like; And methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhex Siloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine , Propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclo Hexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3 -Amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine It includes aliphatic amines, such as.
    [329] Among the amine compounds exemplified above, particular preference is given to aniline derivatives having at least one amino group and represented by the formula:
    [330] [Formula Ⅷ]
    [331]
    [332] [Wherein, R 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group,
    [333] X 1 and X 2 are independently amino groups or represented by the formula b:
    [334] [Formula b]
    [335] ;
    [336] Y 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO- and -CONH- (wherein n is 1 or 2), and the following Chemical Formula a Is a group selected from the group consisting of any group represented by:
    [337] [Formula a]
    [338] ].
    [339] As the OH group containing compound which reacts with the isocyanate compound to form at least one urethane group, any compound can be used as long as it contains at least one OH group. The OH group-containing compound is a phenolic compound such as phenol, cresol, xenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octyl Phenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl ) Propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3- Methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl Acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4 '-Methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 3,4-dihydroxy Neyl-4'-methylphenyl sulfone, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone , 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide , 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl Sulfone, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydrate Hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-meth Oxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxy-carbonylaminosalicylic acid and 4-n-octanoyloxy-carbonylaminosalicylic acid. However, as the phenols, having an amino group is not preferable. Since the amino groups are more reactive to isocyanate groups than OH groups, the amino groups react with isocyanate groups prior to the OH group, and in some cases it is difficult to obtain the desired compound.
    [340] In addition, the OH group-containing compound is methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decane Ol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl Alcohols such as alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol and the like; Polyethers such as polypropylene glycol, polytetramethylene ether glycol, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols and the like Polyols; And ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 6-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorocarbon polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythrate Polyols such as lithol, castor-oil-derived polyol, polymeric polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, sucrose and the like.
    [341] The urea-urethane compound used as the developer in each of the twenty-first and twenty-second aspects of the present invention is a urea having a molecular structure in which the number of urea groups (A) and the number of urethane groups (B) satisfy the following formula: Preference is given to urethane compounds:
    [342] 10 (A + B) 3
    [343] [Wherein, each of A and B is an integer of 1 or more].
    [344] The number of urea groups (A) and the number of urethane groups (B) are (A + B) The urea-urethane compound that satisfies 3 (wherein each of A and B is an integer of 1 or more) has at least one urea group (-NHCONH- group) and at least one urethane group (-NHCOO- group) in total of 3 It is a compound which has the molecular structure which exists more than ten.
    [345] The compound has never been reported and is very novel. The novel compounds are useful in the case of recording materials that use recording energy such as heat, pressure and the like.
    [346] The number of urea groups (A) and the number of urethane groups (B) are (A + B) Synthesis of the urea-urethane compound that satisfies 3 (wherein each of A and B is an integer of 1 or more) includes one or more urea groups (-NHCONH- groups) and one or more urethane groups (-NHCOO- groups). It will not restrict | limit especially as long as it is formed in 3 or more and 10 or less in total. The method for producing the urea-urethane compound by reacting an isocyanate compound with an OH group-containing compound and an amine compound is preferred for its ease.
    [347] Specifically, in each of the twenty-first and twenty-second aspects of the present invention, a urea-urethane compound having at least three urea groups and at least one urethane group in total as a urea-urethane compound used as a developer, For example, an isocyanate having at least two isocyanate groups is used as starting material and the entire isocyanate group, except at least one isocyanate group, is reacted with an OH group containing compound to form at least one urethane group, followed by two molecules of the urethane compound obtained Residual isocyanate groups can be obtained by reacting with each other using water to bond each other.
    [348] In addition, a urea-urethane compound having at least three urea groups and at least one urethane group in total, for example, an isocyanate having two or more isocyanate groups is used as a starting material, and the total isocyanate groups except at least one isocyanate group It can be obtained by reacting with an OH group containing compound to form at least one urethane group, reacting the remaining isocyanate group with an amino compound having at least two amino groups to form at least one urea group, and reacting the remaining amino group with the isocyanate compound.
    [349] Further, a urea-urethane compound having at least one urea group and at least three urethane groups in total in total, with the exception of at least one isocyanate group, is first reacted with all the isocyanate groups with an amine compound to form at least one urea group, and two remaining isocyanate groups It can be obtained by reacting with a compound containing at least OH groups to form at least one urethane group, and then reacting the obtained compound with an isocyanate compound. In this case, a urea-urethane compound having at least one urea group and at least one urethane group in total from 3 to 10 uses an isocyanate compound having at least two isocyanate groups as the isocyanate to be reacted last, and the remaining isocyanate group is selected from at least two OH groups. It can be obtained by repeating the operation of reacting with a containing compound or an amino compound containing two or more amino groups.
    [350] Starting isocyanates are not particularly limited as long as they have two or more isocyanate groups. Starting isocyanates are, for example, p-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane di Isocyanate, o-tolidine diisocyanate, diphenyl ether diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl-carbazole-3,6-diisocyanate, 3,3'-dimethyl -4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanate) thiophosphate, 4,4 ', 4 "-triisocyanato -2,5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene Switch-4-cyclohexyl-comprises a diisocyanate, dicyclohexylmethane diisocyanate and methylcyclohexane diisocyanate.
    [351] As starting isocyanate compounds, further, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT) and toluene diisocyanate equivalents Diisocyanate dimers such as sieves; And diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate can also be used. In addition, water-addition product isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Desmodule L) and; Amine adducts may be used. Also, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171, the contents of which are incorporated herein by reference, at least two isocyanate groups The compound having can be used.
    [352] Particularly preferred examples of such starting isocyanates are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferable. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, can be purchased at low prices, and can also be used as starting isocyanates.
    [353] As the amine compound which reacts with the starting isocyanate to the urea-urethane compound to form at least one urea group, any compound can be used as long as it has at least one amino group. The amine compound is, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethylaniline, N, N- Diethylaniline, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethine Oxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xyldine, 2,4-xyldine, 3,4-xyldine, 2,6-xylidine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, N-methylaniline, N-ethylaniline, N -Propyl aniline, N-butylaniline, N, N-diglycidylaniline, N, N-diglycidyl-o-tol Idine, acetoacetic acid anilide, trimethylphenyl ammonium bromide, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, dia Minodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, o-phenylenediamine m-phenylenediamine, p-phenylenediamine, 2-chloro-p-phenylenediamine, dianisidine, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, Isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m- Aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino-4-meth Sibenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4 -Aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbine Barmoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-methoxyaniline, 4-acetylaminoaniline, 4- (N- Methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4- (N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4- Diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfone, 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2, 5-dime Cy-4-N-phenylsulfamoylaniline, 2-methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl 4-methylaniline, bis [4- (m-aminophenoxy) phenyl] sulphone, bis [4- (p-aminophenoxy) phenyl] sulphone, bis [3-methyl-4- (p-aminophenoxy ) Phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4 '-Diamino-5,5'-dimethoxybiphenyl, 2,2', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-dia Minobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4, 4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodi Aniline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-dia Nodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone , 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4-diaminodiphenylamine, 4,4'-ethylene Dianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2- Bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, 3,3 ', 4,4'-tetraaminodiphenyl ether, 3,3', 4, 4'-tetraaminodiphenyl sulfone, 3,3 ', 4,4'-tetraaminobenzophenone, 3-aminobenzonitrile, 4-phenoxyaniline, 3-phenoxyaniline, 4,4'-methylenebis- o-toluidine, 4,4 '-(p-phenyleneisopropylidene) -bis- (2,6- Ilidine), o-chloro-p-nitroaniline, o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, Metol, 2, 4-diaminophenol, N- (β-hydroxyethyl) -o-aminophenol sulfate, sulfanic acid, methacrylic acid, 4B acid, C acid, 2B acid, p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, m-toluylenediamine, 2-aminothiophenol, 2-amino-3-bromo-5-nitrobenzonitrile, diphenylamine, p-aminodiphenylamine, octylated diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N-diphenyl- p-phenylenediamine, dianisidine, 3,3'-dichlorobenzidine, 4,4'-diami Stilben-2,2'-disulfonic acid, benzylethylaniline, 1,8-naphthalenediamine, sodium naphthionate, Tobias acid, H acid, J acid, phenyl J acid, 1,4-diamino Aromatic amines such as anthraquinone, 1,4-diamino-2,3-dichloroanthraquinone and the like; And 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, acetoguanamine, 2,4-diamino-6 -[2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2,3,5-triaminopyridine, 1-amino Heterocyclic compound amines such as 4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine and the like; And methylamine, ethylamine, dimethylamine, diethylamine, stearylamine, allylamine, diallylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhex Siloxy) propylamine, 3-ethoxypropylamine, diisobutylamine, 3- (diethylamino) propylamine, di-2-ethylhexylamine, 3- (dibutylamino) propylamine, t-butylamine , Propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclo Hexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3 -Amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, ethylenediamine, diethylenetriamine, hexamethylenediamine It includes aliphatic amines, such as.
    [354] Among the amine compounds exemplified above, particular preference is given to aniline derivatives having at least one amino group and represented by the formula:
    [355] [Formula Ⅷ]
    [356]
    [357] [Wherein, R 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group,
    [358] X 1 and X 2 are independently amino groups or represented by the formula b:
    [359] [Formula b]
    [360] ;
    [361] Y 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO- and -CONH- (wherein n is 1 or 2), and the following Chemical Formula a Is a group selected from the group consisting of any group represented by:
    [362] [Formula a]
    [363] ].
    [364] As the OH group containing compound which reacts with isocyanate to form at least one urethane group, any compound can be used as long as it contains at least one OH group. The OH group-containing compound is a phenol, such as phenol, cresol, xenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol, 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 2,2-bis (4-hydroxyphenyl) propane , 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxy Catechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, p, p'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate , Bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'- Methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 3,4-dihydroxyphenyl-4'- Tylphenyl sulfone, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-iso Propylphenyl-4'-hydroxyphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4 '-Dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4' -Dihydroxy-diphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide, bis (4- (2-hydroxy) phenyl) sulfone, 2 , 4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylynilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-Chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydrate Hydroxybenzoate), hexyl 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, stearyl gallate, lauryl gallate, methyl gallate, 4-methoxyphenol, 4- (Benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octa Noyloxysalicylic acid, 4-n-octyloxy-carbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid, and the like. However, as the phenols, having an amino group is not preferable. Since the amino groups are more reactive to isocyanate groups than OH groups, the amino groups react with isocyanate groups prior to the OH group, and in some cases it is difficult to obtain the desired compound. In addition, the OH group-containing compound is methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol, 1-decane Ol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propen-1-ol, benzyl Alcohols such as alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol and the like; Polyethers such as polypropylene glycol, polytetramethylene ether glycol, adipate-derived polyols, epoxy-modified polyols, polyether ester polyols, polycarbonate polyols, polycaprolactone diols, phenolic polyols, amine-modified polyols and the like Polyols; And ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 6-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorocarbon polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythrate Polyols such as lithol, castor-oil-derived polyol, polymeric polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, sucrose and the like.
    [365] As the urea-urethane compound used as a developer in each of the twenty-first and twenty-second aspects of the present invention, a urea-urethane compound represented by any of the following formulas (I) to (V) is preferable:
    [366]
    [367] [Wherein X and Z are independently aromatic compound residues, heterocyclic compound residues or aliphatic compound residues, and each residue may have one or more substituents,
    [368] Y 0 is a group selected from the group consisting of tolylene group, xylylene group, naphthylene group, hexamethylene group, and -φ-CH 2 -φ- group (wherein -φ- is phenylene group) ;
    [369]
    [370] [Wherein X and Y are independently aromatic compound residues, heterocyclic compound residues or aliphatic compound residues, and each residue may have one or more substituents];
    [371]
    [372] [Wherein X and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue,
    [373] α is a residue having a valency of 2 or more,
    [374] n is an integer of 2 or more,
    [375] Each residue may have one or more substituents;
    [376]
    [377] [Wherein, Z and Y are independently an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue,
    [378] β is a residue having two or more valences,
    [379] n is an integer of 2 or more,
    [380] Each residue may have one or more substituents;
    [381] [Formula Ⅴ]
    [382]
    [383] [In formula, it is preferable that the hydrogen atom of each benzene ring is substituted by the substituent which is an aromatic compound residue, an aliphatic compound residue, and a heterocyclic compound residue. However, the said substituent is a nitro group, a hydroxyl group, a carboxyl group, a nitroso group. , Nitrile group, carbamoyl group, ureido group, isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom, each moiety may have one or more substituents,
    [384] γ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH- (wherein n is 1 or 2), and The group is selected from the group consisting of any of the groups shown, or does not exist:
    [385] [Formula a]
    [386] ];
    [387] [Formula VI]
    [388]
    [389] [In formula, it is preferable that the hydrogen atom of each benzene ring is substituted by the substituent which is an aromatic compound residue, an aliphatic compound residue, and a heterocyclic compound residue. However, the said substituent is a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group. , Sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom, The residue may have one or more substituents,
    [390] δ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C (CF 3 ) or a group selected from the group consisting of 2 -and -CR 2 R 3 -wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2;
    [391]
    [392] [Wherein X, Y and Z are independently aromatic compound residues, heterocyclic compound residues or aliphatic compound residues, each residue may have one or more substituents, and each of X, Y and Z is an aromatic compound residue or Preferably a heterocyclic compound moiety].
    [393] In addition, the urea-urethane compounds of the formulas (I) to (I) are very novel. The novel compounds are useful in the case of recording materials that use recording energy such as heat, pressure and the like.
    [394] The method for producing the urea-urethane compound of formula (I), which is used in each of the twenty-first and twenty-second aspects of the present invention, is not limited. The compound can be obtained, for example, by reacting an OH group containing compound of formula (VII) with an isocyanate compound of formula (VII) and an amine compound of formula (XI), for example according to Scheme A below:
    [395]
    [396]
    [397]
    [398] [Wherein X and Z are independently aromatic compound residues, heterocyclic compound residues or aliphatic compound residues, and each residue may have one or more substituents,
    [399] Y 0 is a group selected from the group consisting of tolylene group, xylylene group, naphthylene group, hexamethylene group, and -φ-CH 2 -φ- group (wherein -φ- is phenylene group),
    [400] As used herein, the term "aliphatic" includes the term "alicyclic";
    [401] .
    [402] The method for producing the urea-urethane compound of formula (II), which is used in each of the twenty-first and twenty-second aspects of the present invention, is not limited. The compound can be obtained, for example, by reacting an OH group containing compound of formula (X) with an isocyanate compound of formula (XII) and water, for example according to Scheme B below:
    [403]
    [404] [Wherein Y is an aromatic compound residue, a heterocyclic compound residue or an aliphatic compound residue, each residue may have one or more substituents];
    [405] .
    [406] The method for producing the urea-urethane compound of formula III, which is used in each of the twenty-first and twenty-second aspects of the present invention, is not limited. The compound can be obtained, for example, by reacting an OH group-containing compound of formula (VII) with an isocyanate compound of formula (XII) and an amine compound of formula (XIII) below, for example, according to Scheme C or Scheme D below. :
    [407]
    [408] [Wherein α is a residue having a valence of at least 2, and n is an integer of at least 2;
    [409]
    [410] .
    [411] The method for producing the urea-urethane compound of formula (IV), which is used in each of the twenty-first and twenty-second aspects of the present invention, is not limited. The compound can be obtained, for example, by reacting an amine compound of formula (XI) with an isocyanate compound of formula (XII) and an OH group containing compound of formula (XIV), for example, according to Scheme E or Scheme F below. :
    [412]
    [413] [Wherein β is a residue having a valency of 2 or more, n is an integer of 2 or more];
    [414]
    [415] .
    [416] The compounds of the formulas (VII) to (XIV), which can be used in the synthesis of the urea-urethane compounds of the above formulas (I) to (IV), are described in more detail below.
    [417] The OH group-containing compound of formula (VIII) is not particularly limited as long as it has at least one OH group. The compound is, for example, mono phenols such as phenol, cresol, xenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol, p-tert-octylphenol , 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, p-nitrophenol, o-chlorophenol, p-chlorophenol, 4-phenylphenol, 4-hydroxyphenyl-4 '-Methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylic Anilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1 , 5-bis (4'-hydroxybenzoate), 1,6-bis (4'-hydroxybenzoate), dimethyl 3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyloxy) phenol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid , 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxycarbonylaminosalicylic acid and 4-n- Octanoyloxycarbonylaminosalicylic acid and the like. In addition, the compound of formula (VIII) is diphenols such as 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane , 2,2-bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, 4-phenylphenol, 4,4'-biphenol, 4-cumylphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone , Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2- Methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2 , 2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxydiphenyl Min, the bis or the like (4-hydroxy-3-methylphenyl) sulfide. However, as the OH group-containing compound, it is not preferable to have an amino group. When amino groups are present with OH groups, since the amino groups are more reactive to isocyanate groups than OH groups, the amino groups react with isocyanate groups prior to OH groups, and in some cases, it is difficult to obtain the desired compound. In addition, the compounds of formula (VIII) are polyhydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, isopropanol, isobutanol, isopentanol, 2-ethyl-1-hexanol , 1-decanol, 2-pentanol, 3-hexanol, tert-butanol, tert-amyl alcohol, methyl cellosolve, butyl cellosolve, methyl carbitol, allyl alcohol, 2-methyl-2-propene-1 -Ol, benzyl alcohol, 4-pyridinemethanol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, cyclohexyl methanol, cyclopentanol, 2-chloroethanol, 1-chloro-3-hydroxypropane, glycerin, glycerol, etc. It includes. As the compound of the formula (VIII), it is also known as polypropylene glycol, polytetramethylene ether glycol, adipate-derived polyol, epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, phenolic polyol, amine Polyether polyols such as modified polyols; And ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 6-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorocarbon polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythrate Polyols such as lithol, castor-oil-derived polyol, polymeric polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, sucrose and the like. Among these, monophenols are used preferably.
    [418] Isocyanate compounds of formula (VIII) include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, m-xylylene diisocyanate, and the like. Include. Among these, toluene diisocyanate is preferable.
    [419] The isocyanate compound of the formula (XII) is not particularly limited as long as it has two or more isocyanate groups. The compound is, for example, p-phenylene diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane di Isocyanate, o-tolidine diisocyanate, 1,5-naphthylene diisocyanate, dianisidine diisocyanate, 9-ethyl-carbazole-3,6-diisocyanate, 3,3'-dimethyl-4,4'- Diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, tris (4-phenylisocyanato) thiophosphate, 4,4 ', 4 "-triisocyanato-2, 5-dimethoxytriphenylamine, 4,4 ', 4 "-triisocyanatotriphenylamine, m-xylylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, isopropylidene bis-4-cyclohexyl- Isocyanate, Dicyclo Hexylmethane diisocyanate and methylcyclohexane diisocyanate. As isocyanate compounds of the formula (XII), there are also, for example, N, N '-(4,4'-dimethyl-3,3'-diphenyldiisocyanato) uretodione (trade name: Desmodule TT) and toluene di Diisocyanate dimers such as isocyanate dimers; And diisocyanate trimers such as 4,4 ', 4 "-trimethyl-3,3', 3" -triisocyanato-2,4,6-triphenylcyanurate can also be used. In addition, water-addition product isocyanates such as toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adduct of toluene diisocyanate (trade name: Desmodule L); And amine adducts may be used.
    [420] Further, among the isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and the specification of JP-A-10-95171, compounds having two or more isocyanate groups can be used. A particularly preferred example of the isocyanate compound of formula (XII) is toluene diisocyanate.
    [421] The amine compound of formula (XI) is not particularly limited as long as it has at least one amino group. The compound is, for example, aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, 2,4-dimethoxyaniline, 2,5- Dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, p-aminobenzoic acid, o-aminophenol, m-aminophenol, p-aminophenol, 2,3-xyldine, 2,4-xyl Dine, 3,4-xyldine, 2,6-xyldine, 4-aminobenzonitrile, anthranilic acid, p-cresidine, 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloro Aniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, α-naphthylamine, aminoanthracene, o-ethylaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline, methyl p -Aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-aminobenzoate, benzyl p-aminobenzoate , o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino-N-methylbenzamide, 3-amino- 4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, p- (N-phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) Carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N-phenylcarbamoyl) -aniline, 2-methoxy-5- [N -(2'-methyl-3'-chlorophenyl) carbamoyl] aniline, 2-methoxy-5- [N- (2'-chlorophenyl) carbamoyl] aniline, 5-acetylamino-2-meth Methoxyaniline, 4-acetylaminoaniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, 4-sulfamoylaniline, 3-sulfamoylaniline, 2- (N-ethyl-N-phenyl Aminosulfonylaniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfin , 2-chloro-5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline, 2,5-dimethoxy-4-N-phenylsulfamoylaniline, 2-meth Methoxy-5-benzylsulfonylaniline, 2-phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, o-chloro-p-nitroaniline , o-nitro-p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniline, 2-amino-4-chlorophenol, o-nitroaniline, m-nitroaniline, p Nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine, 2-amino-5-nitrobenzonitrile, sulfanilic acid, methalinic acid, 4B acid, C acid, 2B acid, p-fluoro Aniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino- Aromatic monoamines such as 3-bromo-5-nitrobenzonitrile; And 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'- Dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis [4- (m-aminophenoxy) Phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4 ' -Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2, 2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4 '-Diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4, 4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl Le, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenylmethane, bis (3- Amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diamino Diphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldi Benzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2'-bis (4-aminophenoxyphenyl) propane, 4,4'-bis Aromatic diamines such as (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine and the like. In addition, the amine compound of the formula (XI) is, for example, 3-amino-1,2,4-triazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, α-amino-ε-caprolactam, Acetoguanamine, 2,4-diamino-6- [2'-methylimidazolyl- (1)] ethyl-S-triazine, 2,3-diaminopyridine, 2,5-diaminopyridine, 2 Such as 3,5-triaminopyridine, 1-amino-4-methylpiperazine, 1- (2-aminoethyl) piperazine, bis (aminopropyl) piperazine, N- (3-aminopropyl) morpholine, etc. Heterocyclic compound amines; And methylamine, ethylamine, stearylamine, allylamine, isopropylamine, 2-ethylhexylamine, ethanolamine, 3- (2-ethylhexyloxy) propylamine, 3-ethoxypropylamine, 3- ( Diethylamino) propylamine, 3- (dibutylamino) propylamine, t-butylamine, propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3-methoxypropylamine, Methylhydrazine, 1-methylbutylamine, methanediamine, 1,4-diaminobutane, cyclohexanemethylamine, cyclohexylamine, 4-methylcyclohexylamine, 2-bromoethylamine, 2-methoxyethylamine, 2-ethoxymethylamine, 2-amino-1-propanol, 2-aminobutanol, 3-amino-1,2-propanediol, 1,3-diamino-2-hydroxypropane, 2-aminoethanethiol, Aliphatic amines such as ethylenediamine, diethylenetriamine, hexamethylenediamine and the like. Among these, aromatic monoamines are used preferably.
    [422] The amine compound of formula (XIII) is not particularly limited as long as it has two or more amino groups. The compound is, for example, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,5-diaminochlorobenzene, diaminodiphenyl Ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, tolidine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulfone, bis [4- (p-aminophenoxy) phenyl] sulfone, bis [3-methyl-4- (p-aminophenoxy) phenyl] sulfone, 3,3'- Dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diamino-5,5'- Dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2,4'-diaminobiphenyl, 2,2'-dia Minobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2, 2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3,4'-dia Minodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl Sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-dia Mino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (4-aminophenoxyphenyl) Propane, 4,4'-bis (4-aminophenoxy) diphenyl, dianisidine, 3,3'-dichlorobenzidine, tolidine base, o-phenylenediamine, m-phenylenediamine, p-phenylene Aromatic amines such as diamine. Among the amine compounds exemplified above, particularly preferred are aniline derivatives having two or more amino groups and represented by the formula:
    [423] [Formula Ⅷ]
    [424]
    [425] [Wherein, R 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group,
    [426] X 1 and X 2 are independently amino groups or groups represented by the formula (b):
    [427] [Formula b]
    [428] ;
    [429] Y 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO- and -CONH- (wherein n is 1 or 2), and the following Chemical Formula a Is a group selected from the group consisting of any group represented by:
    [430] [Formula a]
    [431] ].
    [432] The OH group-containing compound of formula (XIV) is not particularly limited as long as it has at least two OH groups. The compound is, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2- Bis (hydroxyphenyl) heptane, catechol, 3-methylcatechol, 3-methoxycatechol, pyrogallol, hydroquinone, methylhydroquinone, p, p'-biphenol, butyl bis (4-hydroxyphenyl) acetate , Benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) Sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-allyl-4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfone Feed, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane , 4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4-hydroxy-3-methylphenyl) sulfide and the like Diphenols are included. However, it is not preferable to have an amino group as the diphenols. Since the amino groups are more reactive to isocyanate groups than OH groups, the amino groups react with isocyanate groups prior to the OH group, and in some cases it is difficult to obtain the desired compound. In addition, the OH group-containing compound of the formula (XIV) is polypropylene glycol, polytetramethylene ether glycol, adipate-derived polyol, epoxy-modified polyol, polyether ester polyol, polycarbonate polyol, polycaprolactone diol, phenol Polyether polyols such as polyols and amine-modified polyols; And ethylene glycol, diethylene glycol, 1,3-propanediol, 1,2-propanediol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 , 6-hexane glycol, 1,9-nonanediol, acrylic polyol, fluorocarbon polyol, polybutadiene polyol, polyhydroxy polyol, trimethylolpropane, trimethylolethane, hexanetriol, phosphoric acid, neopentyl glycol, pentaerythrate Polyols such as lithol, castor-oil-derived polyol, polymeric polyol, methylpentanediol, halogen-containing polyol, phosphorus-containing polyol, ethylenediamine, α-methylglucoside, sorbitol, sucrose and the like.
    [433] The method for producing the urea-urethane compound of formula V, which is used in each of the twenty-first and twenty-second aspects of the present invention, is not limited. The compound can be obtained, for example, by reacting a monophenol compound with an aromatic diisocyanate compound and an amine compound of formula XV, for example according to Scheme G or Scheme H below:
    [434]
    [435] [In formula, it is preferable that the hydrogen atom of each benzene ring is substituted by the substituent which is an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. However, the said substituent is a nitro group, a hydroxyl group, a carboxyl group, a nitroso group. , Nitrile group, carbamoyl group, ureido group, isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom, each moiety may have one or more substituents,
    [436] γ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH- (wherein n is 1 or 2), and The group is selected from the group consisting of any of the groups shown, or does not exist:
    [437] [Formula a]
    [438] ];
    [439]
    [440] .
    [441] The method for producing the urea-urethane compound of formula VI, which is used in each of the twenty-first and twenty-second aspects of the present invention, is not limited. The compound can be obtained, for example, by reacting an aniline derivative with an aromatic diisocyanate compound and a dihydroxy compound of formula XVI, for example according to Scheme J or Scheme K below:
    [442] [Formula XVI]
    [443]
    [444] [In formula, it is preferable that the hydrogen atom of each benzene ring is substituted by the substituent which is an aromatic compound residue, an aliphatic compound residue, or a heterocyclic compound residue. However, the said substituent is a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group. , Sulfamoyl group, carboxyl group, nitroso group, amino group, oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom, The residue may have one or more substituents,
    [445] δ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C (CF 3 ) 2 -and -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2) or none exists;
    [446]
    [447] .
    [448] The compounds usable in the synthesis of the urea-urethane compounds of the formula (V) or (VI), used in each of the twenty-first and twenty-second aspects of the invention, are described in detail below.
    [449] The phenolic compound usable for the synthesis of the urea-urethane compound of Formula V is not particularly limited as long as it has at least one OH group on the benzene ring. In addition, the hydrogen atoms of the benzene ring may be substituted with substituents other than OH groups, that is, aromatic compound residues, aliphatic compound residues, heterocyclic compound residues, nitro groups, carboxyl groups, hydroxyl groups, nitroso groups, nitrile groups, and carboxes. It may be substituted with a bamoyl group, ureido group, isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom.
    [450] Preferred examples of the phenol-based compound include phenols such as phenol, cresol, xylenol, p-ethylphenol, o-isopropylphenol, resorcinol, p-tert-butylphenol and p-tert-octylphenol , 2-cyclohexylphenol, 2-allylphenol, 4-indanol, thymol, 2-naphthol, nitro substituted phenols (eg p-nitrophenol), halogen substituted phenols (eg o-chlorophenol and p-chlorophenol ), 4-phenylphenol, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4-hydroxy-4'-isopropoxydiphenyl sulfone, phenyl salicylate, salicylic Anilide, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, dimethyl-3-hydroxyphthalate, 4-methoxyphenol, 4- (benzyl Oxy) Nol, 4-hydroxybenzaldehyde, 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n-octyloxy-carbonylaminosalicylic acid and 4-n-octanoyloxycarbonylaminosalicylic acid and the like. In addition, as the phenolic compound, a phenol having at least one substituent including a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group, an isocyanate group, a mercapto group, a sulfo group, a sulfamoyl group, and the like. System compounds can be used. However, as the phenols, having an amino group is not preferable. Since the amino groups are more reactive to isocyanate groups than OH groups, the amino groups react with isocyanate groups prior to the OH group, and in some cases it is difficult to obtain the desired compound.
    [451] The aromatic diisocyanate compound usable for the synthesis of the urea-urethane compound of the formula (V) or (VI) is not particularly limited as long as it has two isocyanate groups bonded to its benzene ring. The aromatic diisocyanate compound is, for example, p-phenylene diisocyanate, 2,5-dimethoxy-benzene-1,4-diisocyanate, 2,4-toluene diisocyanate and 2,6-toluene diisocyanate Include. Particularly preferred examples of aromatic isocyanate compounds are toluene diisocyanates. Of the toluene diisocyanates, 2,4-toluene diisocyanate is preferable. In addition to 2,4-toluene diisocyanate, mixtures of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate are generally commercially available, can be purchased at low prices, and can also be used as aromatic diisocyanate compounds. . The mixture of toluene diisocyanate isomers is liquid at room temperature.
    [452] Diamine compounds of formula (XV) usable for the synthesis of urea-urethane compounds of formula (V) are, for example, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminobenz Anilide, 3,5-diaminochlorobenzene, diaminodiphenyl ether, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodi Phenylmethane, tolidine base, dianisidine, bis [4- (m-aminophenoxy) phenyl] sulphone, bis [4- (p-aminophenoxy) phenyl] sulphone, bis [3-methyl-4- ( p-aminophenoxy) phenyl] sulfone, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'- Dichloro-4,4'-diamino-5,5'-dimethoxybiphenyl, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, o-tolidine sulfone, 2 , 4'-diaminobiphenyl, 2,2'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3 ' -Dichloro-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-di Aminobiphenyl, 4,4'-thiodaniline, 2,2'-dithiodaniline, 4,4'-dithiodaniline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodi Phenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl methane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chlorophenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-dia Minodiphenylmethane, 4,4'-diaminodiphenylamine, 4,4'-ethylenedianiline, 4,4'-diamino-2,2'-dimethyldibenzyl, 3,3'-diaminobenzo Phenone, 4,4'-diaminobenzophenone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy Benzene, 9,9-bis (4-aminophenyl) fluorene, 2,2'-bis (4-aminophenoxyphenyl) propane, 4,4'-bis (4-aminophenoxy) diphenyl, Aromatic diamines such as dianisidine and 3,3'-dichlorobenzidine It includes.
    [453] The aniline derivative usable for the synthesis of the urea-urethane compound of formula VI is not particularly limited as long as it is an aniline compound having at least one amino group on the benzene ring. In addition, the hydrogen atoms of the benzene ring include aromatic compound residues, aliphatic compound residues, heterocyclic compound residues, hydroxyl groups, nitro groups, nitrile groups, carbamoyl groups, sulfamoyl groups, carboxyl groups, nitroso groups, and amino groups. , Oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom.
    [454] Preferred examples of the aniline compound include aniline, o-toluidine, m-toluidine, p-toluidine, o-anisidine, p-anisidine, p-phenetidine, N, N-dimethyl-p-phenylenediamine, N, N-diethyl-p-phenylenediamine, 2,4-dimethoxyaniline, 2,5-dimethoxyaniline, 3,4-dimethoxyaniline, p-aminoacetanilide, carboxy substituted aniline (e.g. p -Aminobenzoic acid), hydroxyl substituted aniline (e.g. o-aminophenol, m-aminophenol, 2-amino-4-chlorophenol and p-aminophenol), 2,3-xylidine, 2,4-xylidine , 3,4-xylidine, 2,6-xyldine, nitrile substituted aniline (e.g. 4-aminobenzonitrile), anthranilic acid, p-cresidine, halogen substituted aniline (e.g. 2,5-dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2,4,5-trichloroaniline, o-chloroaniline, m-chloroaniline and p-chloroaniline), α-naph Tylamine, Aminoant Lacene, o-ethylaniline, methyl p-aminobenzoate, ethyl p-aminobenzoate, n-propyl p-aminobenzoate, isopropyl p-aminobenzoate, butyl p-aminobenzoate, dodecyl p-amino Benzoate, benzyl p-aminobenzoate, o-aminobenzophenone, m-aminoacetophenone, p-aminoacetophenone, m-aminobenzamide, o-aminobenzamide, p-aminobenzamide, p-amino- N-methyl-benzamide, 3-amino-4-methylbenzamide, 3-amino-4-methoxybenzamide, 3-amino-4-chlorobenzamide, carbamoylaniline {eg, p- (N- Phenylcarbamoyl) aniline, p- [N- (4-chlorophenyl) carbamoyl] aniline, p- [N- (4-aminophenyl) carbamoyl] aniline, 2-methoxy-5- (N -Phenylcarbamoyl) aniline, 2-methoxy-5- [N- (2'-methyl-3'-chlorophenyl) carbamoyl] aniline and 2-methoxy-5- [N- (2'- Chlorophenyl) carbamoyl] aniline}, 5-acetylamino-2 -Methoxyaniline, 4-acetylaminoaniline, 4- (N-methyl-N-acetylamino) aniline, 2,5-diethoxy-4- (N-benzoylamino) aniline, 2,5-dimethoxy-4 -(N-benzoylamino) aniline, 2-methoxy-4- (N-benzoylamino) -5-methylaniline, sulfamoylaniline (e.g. 4-sulfamoylaniline, 3-sulfamoylaniline, 2-chloro- 5-N-phenylsulfamoylaniline, 2-methoxy-5-N, N-diethylsulfamoylaniline and 2,5-dimethoxy-4-N-phenylsulfamoylaniline), 2- (N-ethyl- N-phenylaminosulfonyl) aniline, 4-dimethylaminosulfonylaniline, 4-diethylaminosulfonylaniline, sulfatiazole, 4-aminodiphenyl sulfone, 2-methoxy-5-benzylsulfonylaniline, 2 -Phenoxysulfonylaniline, 2- (2'-chlorophenoxy) sulfonylaniline, 3-anilinosulfonyl-4-methylaniline, nitro substituted aniline (e.g. o-chloro-p-nitroaniline, o-nitro -p-chloroaniline, 2,6-dichloro-4-nitroaniline, 5-chloro-2-nitroaniyl o-nitroaniline, m-nitroaniline, p-nitroaniline, 2-methyl-4-nitroaniline, m-nitro-p-toluidine and 2-amino-5-nitrobenzonitrile), p-fluoroaniline, o-fluoroaniline, 3-chloro-4-fluoroaniline, 2,4-difluoroaniline, 2,3,4-trifluoroaniline, m-aminobenzotrifluoride, 2-amino-3- Bromo-5-nitrobenzonitrile and the like.
    [455] As aniline derivatives, aniline derivatives having one or more substituents, including carboxyl groups, nitroso groups, oxyamino groups, nitroamino groups, hydrazino groups, ureado groups, isocyanate groups, mercapto groups, sulfo groups and the like, are also Can be used.
    [456] Dihydroxy compounds of formula XVI usable for the synthesis of urea-urethane compounds of formula VI include, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis (hydroxyphenyl) heptane, 4,4'-biphenol, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxy Phenyl) acetate, bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (2-allyl- 4-hydroxyphenyl) sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfide, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4,4'-dihydroxy-diphenylmethane, 3,3'-dihydroxydi Diphenols such as phenylamine, bis (4-hydroxy-3-methylphenyl) sulfide and the like. However, as said diphenols, having an amino group is not preferable. Since the amino groups are more reactive to isocyanate groups than OH groups, the amino groups react with isocyanate groups prior to the OH group, and in some cases, it is difficult to obtain the desired compound.
    [457] The method for synthesizing the urea-urethane compound of the formula (VII) used in each of the twenty-first and twenty-second aspects of the present invention is not particularly limited. The compound can be obtained, for example, by reacting an OH group containing compound of formula (X) with an isocyanate compound of formula (XII) and an amine compound of formula (XI), for example according to the following reaction scheme L:
    [458] .
    [459] Substituent X bound to the urethane group of the urea-urethane compound of formula (VII) is an alkyl group, alkenyl group, phenyl group, cycloalkyl group, amide group, alkoxyl group, nitro group, nitroso group, nitrile group, toluenesulfonyl Groups, methanesulfonyl groups, acetyl groups, halogen atoms, formyl groups, dialkylamino groups and isocyanate groups are preferred.
    [460] Among the above-mentioned urea-urethane compounds of the formulas (I) to (X) which are developer agents, the compounds of the formulas (II) to (VI) are preferred, and the compounds of the formulas (V) to (VI) are particularly preferred.
    [461] Also particularly preferred are compounds of formula XX or XXI.
    [462] [Formula XX]
    [463]
    [464] [Formula XXI]
    [465]
    [466] In the case of the urea-urethane compounds used as the developer in each of the twenty-first and twenty-second aspects of the present invention, and in the case of the compounds of the formulas (I) to (IV) and (V) as the developer, the residues bound to their urea groups or urethane groups are aliphatic compound residues. If so, color development and print preservation ability are lowered. Therefore, it is preferable that the residue bonded to the urea group or the urea group is an aromatic compound residue or a heterocyclic compound residue. However, the decrease in color development concentration and print preservation ability that can be caused by the introduction of aliphatic compound residues is reduced by increasing the total number of urea groups and urethane groups. In the case of the compounds of the formulas (III) and (IV), even if an aliphatic compound residue is present in the residue bonded to the urea group or the urethane group, almost no problem for the performance characteristics is caused.
    [467] The urea-urethane compounds used in each of the twenty-first and twenty-second aspects of the present invention mix the aforementioned isocyanates with the corresponding reactants in an organic solvent or without a solvent, and after reacting them, the obtained crystals are collected by filtration. As each reactant, one or more compounds may be used depending on the purpose. As the solvent, any solvent can be used as long as it does not react with the isocyanate group and the functional group of the reactant. The solvent includes, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated alicyclic hydrocarbons and ketones. Particular preference is given to methyl ethyl ketone, toluene and the like, in which the isocyanate is dissolved and the solubility of the reaction product is low. The reaction product obtained by the above reaction operation is not always a single compound and in some cases is obtained as a mixture of compounds having different positions of substituents.
    [468] Specific examples of the urea-urethane compound used in each of the twenty-first and twenty-second aspects of the present invention are the following compounds (E-1) to (E-43).
    [469]
    [470]
    [471]
    [472]
    [473]
    [474]
    [475]
    [476]
    [477]
    [478]
    [479]
    [480] Urea-urethane compounds used as the developer of the present invention are usually colorless or light colored compounds that are solid at room temperature.
    [481] The molecular weight of the urea-urethane compound used as the developer of the present invention is preferably 5000 or less, and more preferably 2000 or less.
    [482] Preferably the sum total of the number of urea groups and urethane groups of the urea-urethane compound used as a developer of this invention is 20 or less, More preferably, it is 10 or less. The ratio of urea groups / urethane groups in the molecular structure of the urea-urethane compound is preferably 1: 3 to 3: 1, especially 1: 2 to 2: 1.
    [483] In order to produce the recording material using the urea-urethane compound as the developer, one kind of urea-urethane compound, or a combination of two or more urea-urethane compounds may be used if necessary.
    [484] When used in a thermal recording material, it is preferable that the urea-urethane compound has a melting point. Melting | fusing point of the urea urethane compound used as a developer of this invention becomes like this. Preferably it is the range of 40 to 500 degreeC, especially the range of 60 to 300 degreeC.
    [485] The colorless or pale dye precursor used in the twenty-second aspect of the present invention is a compound well known as a color developing agent used in the pressure-sensitive recording material and the thermal recording material, and is not particularly limited. As a dye precursor, a leuco dye is especially preferable, and a triarylmethane type leuco dye, a fluorane type leuco dye, a fluorene type leuco dye, a diphenylmethane type leuco dye, etc. are more preferable. Representative examples of leuco dyes are given below.
    [486] (1) triaryl methane compounds
    [487] 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3-bis (p-dimethylaminophenyl) phthalide, 3- (p-dimethylaminophenyl) -3- (1,2-dimethylindol-3-yl) phthalide, 3- (p-dimethylaminophenyl) -3- (2-methylindol-3-yl) phthalide, 3- (p-dimethylamino Phenyl) -3- (2-phenylindol-3-yl) phthalide, 3,3-bis (1,2-dimethylindol-3-yl) -5-dimethylaminophthalide, 3,3-bis ( 1,2-dimethylindol-3-yl) -6-dimethylaminophthalide, 3,3-bis (9-ethylcarbazol-3-yl) -5-dimethylaminophthalide, 3,3-bis (2-phenylindol-3-yl) -5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3- (1-methylpyrrole-2-yl) -6-dimethylaminophthalide and the like.
    [488] (2) diphenylmethane compounds
    [489] 4,4'-bis-dimethylaminophenylbenzhydryl benzyl ether, N-halophenylleucoauramin, N-2,4,5-trichloro-phenylleucoauramin, etc .;
    [490] (3) xanthene compound
    [491] Rhodamine B anilinolactam, Rhodamine Bp-chloroanilinolactam, 3-dimethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl- Fluorane, 3-diethylamino-7-methyl-fluorane, 3-diethylamino-7-chloro-fluorane, 3-diethylamino-7-dibenzylaminofluorane, 3-diethylamino-6 -Methyl-7-chlorofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7-phenylfluorane, 3-diethylamino-6-methyl-7-anilinofluorane , 3-diethylamino-6-methyl-7-p-methylanilinofluorane, 3-diethylamino-6-chloro-7-methylfluorane, 3-diethylamino-7- (3,4- Dichloroanilino) fluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (o, p-dimethylanilino) fluoran, 3 -(N-ethyl-N-tolyl) amino-6-methyl-7-phenethylfluorane, 3-diethylamino-7- (4-nitroanilino) flu Oran, 3-diethylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-diethylamino-6-methyl-7- (o-chloroanilino) fluorane, 3 -Diethylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-diethylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-diethylamino- 6-methyl-7- (pn-butylanilino) fluorane, 3-diethylamino-6-methyl-7-n-octylaminofluorane, 3-diethylamino-6-chloro-7-anilinofluor Column, 3-diethylamino-6-ethoxyethyl-7-anilinofluorane, 3-diethylamino-benzo [a] fluorane, 3-diethylamino-benzo [c] fluorane, 3-di Ethylamino-6-methyl-7-benzylaminofluorane, 3-diethylamino-6-methyl-7-dibenzylaminofluoran, 3-diethylamino-7-di (p-methylbenzyl) aminofluoran , 3-diethylamino-6-methyl-7-diphenylmethylaminofluorane, 3-diethylamino-7-dinaphthylmethylaminofluorane, 10-diethyla No-4-dimethylaminobenzo [a] fluorane, 3-diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7- (m-trichloroanilino) fluorane, 3-diethylamino-7- (o-chloroanilino) fluorane, 3-dibutylamino-7- (o-chloro-anilino) fluorane, 3-diethylamino-6-methyl-7- ( 2 ', 4'-dimethylanilino) fluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3-morpholino-7 -(N-propyltrifluoromethylanilino) fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7- (N-benzyl-tri Fluoromethylanilino) fluorane, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluorane, 3-diethylamino-5-chloro-7- (α-phenylethylamino) fluoro Column, 3- (N-ethyl-Np-toludino) -7- (α-phenylethylamino) fluorane, 3-diethylamino-7- (o-methoxycarbonylphenylethyl) fluorane, 3 -Die Tylamino-5-methyl-7- (α-phenylethylamino) fluorane, 3-diethylamino-7-piperidinoaminofluorane, 2-chloro-3- (N-methyltoludino) -7 -(pN-butylanilino) fluorane, 3- (N-ethyl-N-cyclohexylamino) -5,6-benzo-7-α-naphthylamino-4'-bromofluorane, 3-di Ethylamino-6-methyl-7-mesitydino-4 ', 5'-benzofluoran, 3-dibutylamino-6-methyl-fluorane, 3-dibutylamino-6-methyl-7-chlorofluoro Column, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-p-methylanilinofluorane, 3-dibutylamino-6-methyl-7 -(o, p-dimethylanilino) fluorane, 3-dibutylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-dibutylamino-6-methyl-7- (o-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-dibutylamino-6-methyl-7- (o-fluoroaniyl Lino) fluorane, 3-dibutylamino-6 -Methyl-7- (pn-butylanilino) fluorane, 3-dibutylamino-6-methyl-7-n-octylaminofluorane, 3-dibutylamino-6-chloro-7-anilinofluorane , 3-dibutylamino-6-ethoxyethyl-7-anilinofluorane, 3-di-n-pentylamino-6-methyl-7-anilinofluorane, 3-di-n-pentylamino-6 -Methyl-7- (o, p-dimethylanilino) fluorane, 3-di-n-pentylamino-6-methyl-7- (m-trifluoromethylanilino) fluorane, 3-di-n -Pentylamino-6-methyl-7- (o-chloroanilino) fluorane, 3-di-n-pentylamino-6-methyl-7- (p-chloroanilino) fluorane, 3-di-n -Pentylamino-6-methyl-7- (o-fluoroanilino) fluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7- Anilinofluorane, 3-cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane, 3- (N-methyl-N-isoamylamino) -6-methyl-7- Anilinofluorane, 3- (N-methyl-Nn-propyl Mino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-amylamino) -6-methyl-7-anilinofluorane, 3- (N, N-di-n-amyl Amino) -6-methyl-7-anilinofluorane, 3- (N-methyl-N-isopropylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-Nn-propylamino ) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isopropylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-Nn-butylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isobutylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-Nn-hexylamino)- 6-methyl-7-p-methylanilinofluorane, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7- (o, p-dimethylanilino) fluorane, 3- (N- Ethyl-Nn-hexylamino) -6-methyl-7- (m-trifluoromethylanilino) fluorane, 3- (N-ethyl-Nn-hexylamino) -6-methyl-7- (o-chloro Anilino) fluorane, 3- (N-ethyl-N-isoamylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl Mino) -6-chloro-7-anilinofluorane, 3- (N-ethyl-N-3-methylbutylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-Np- Toludino--6-methyl-7-anilinofluorane, 3- (N-ethyl-Np-toluidino) -6-methyl-7- (p-methylanilino) fluorane, 3- (N -Ethyl-Np-toluidino) -6-methyl-7- (o, p-dimethylanilino) fluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino) -6-methyl-7- Anilinofluorane, 3- (N-cyclohexyl-N-methylamino) -7-anilinofluorane, 3- (N-ethyl-N-3-methoxypropylamino) -6-methyl-7-anyl Linofluorane, 3- (N-ethyl-N-3-ethoxypropylamino) -6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-dimethylamino-6-methyl- 7-anilinofluorane, 2- (4-oxahexyl) -3-diethylamino-6-methyl-7-anilinofluorane, 2- (4-oxahexyl) -3-dipropylamino-6- Methyl-7-anilinofluorane, 3,6-bis (diethylamino) -fluorane-γ- (2'-nitro) anilinolactam, 3, 6-bis (diethylamino) -fluorane-γ- (3'-nitro) anilinolactam, 3,6-bis (diethylamino) -fluorane-γ- (4'-nitro) anilinolactam, 3,6-bis (diethylamino) fluorane-γ-anilinolactone and the like.
    [492] (4) thiazine-based compound
    [493] Benzoyl leucomethylene blue, p-nitrobenzoyl leucomethylene blue and the like.
    [494] (5) spiro compounds
    [495] 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3-dichlorospirodinaphthopyran, 3-benzylspirodinaphthopyran, 3-methylnaphtho- (3-methoxybenzo) spiropyran, 3-propylspirobenzopyran and the like.
    [496] In addition, the leuco dyes include, for example, the following compounds capable of absorbing near infrared light: 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dimethylamino-phthal Lead), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3 '-(6'-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro -3 '-(6'-dimethylaminophthalide), 3-dibutylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-dimethylaminophthalide), 3-dibutyl Amino-6-diethylaminofluorene-9-spiro-3 '-(6'-dimethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9-spiro-3'-(6 ' -Diethylaminophthalide), 3-diethylamino-6-dimethylaminofluorene-9-spiro-3 '-(6'-diethylaminophthalide), 3-dibutylamino-6-dimethyl Aminofluorene-9-spiro-3 '-(6'-dimethylaminophthalide), 3,6-bis (diethylamino) fluorene-9-spiro-3'-(6'-di Ethylaminophthalide), 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dibutylaminophthalide), 3-dibutylamino-6-diethylaminoflu Oren-9-spiro-3 '-(6'-diethylaminophthalide), 2-diethylamino-6-dimethylaminofluorene-9-spiro-3'-(6'-dibutylaminophthal Lead), 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7-tetrachlorophthalide and the like.
    [497] Among the leuco salts exemplified above, in view of sensitivity and plasticizer resistance, triarylmethane-based leuco dyes, fluorane-based leuco dyes, fluorene-based leuco dyes and diphenylmethane-based leuco dyes are preferable, and are represented by the following general formulas i or j More preferred are compounds having the structure represented:
    [498] [Formula i]
    [499]
    [500] [Wherein, Y 2 and Y 3 are both an alkyl group or an alkoxyalkyl group,
    [501] Y 4 is a hydrogen atom, an alkyl group or an alkoxy group,
    [502] Each of Y 5 and Y 6 is a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group]; or
    [503] [Formula j]
    [504]
    [505] [Wherein R 5 and R 6 are each a group represented by the following formula (k) or (l):
    [506] [Formula k]
    [507]
    [508] Wherein R 11 to R 15 each represent a hydrogen atom, a halogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 alkoxy group, or each of R 16 and R 17 is a C 1 -C 8 alkyl group; NR 16 R 17 }, or
    [509] [Formula l]
    [510]
    [511] {Wherein, R 18 and R 19 are each a hydrogen atom, a C 1 -C 8 alkyl group, or a phenyl group};
    [512] Each of R 7 to R 10 is a hydrogen atom, a halogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 alkoxy group, or each of R 20 and R 21 is a C 1 -C 8 alkyl group -NR 20 R 21 ].
    [513] The colorless or pale dye precursor may be used in combination of two or more, if necessary.
    [514] The urea-urethane compound, which is a developer, is used in a ratio of preferably 5 to 1000 parts by weight, more preferably 20 to 500 parts by weight, per 100 parts by weight of a colorless or pale dye dye precursor. As a ratio of the urea-urethane compound which is a developing agent, if it is 5 weight part or more, it is enough for a dye precursor to develop. At this ratio, the color development concentration is high. When the ratio of the urea-urethane compound that is a developer is 1000 parts by weight or less, the urea-urethane compound that is a developer is rarely left in excess, which is preferable because it is economically advantageous.
    [515] A urea-urethane compound or urea-urethane composition used as a developer in the nineteenth aspect of the present invention, the first to fourth optional urea-urethane compounds of the present invention, or any of the fifth to twelfth aspects of the present invention. Urea-urethane compositions can be used. The synthesis method of the compound and the composition is as already described in detail in the first to twelfth description of the present invention.
    [516] The storage stability of a composition improves by introducing an isocyanate compound into the coloring composition of this invention. The isocyanate compound introduced into the color developing composition of the present invention relates to a colorless or light colored, aromatic or heterocyclic isocyanate compound which is solid at room temperature. For example, one or more of the following isocyanate compounds are used.
    [517] The isocyanate compound to be introduced is 2,6-dichlorophenyl isocyanate, p-chlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-4,6-di Isocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1-ethoxybenzene-2, 4-diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxylbenzene-1,4-diisocyanate, 2,5-dibutoxybenzene-1,4-diisocyanate, Azobenzene-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene -2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,4'-diisocyanate, 3,3'-dimethoxy-biphenyl-4,4'-diisocyanate, Diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, benzophenone-3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2 , 6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, pyrene-3,8-diisocyanate, naphthalene-1,3,7-triisocyanate, biphenyl-2,4,4'-tri Isocyanate, 4,4 ', 4 "-triisocyanato-2,5-dimethoxytriphenylamine, 4,4', 4" -triisocyanato-triphenylamine, p-dimethylaminophenyl isocyanate, tris (4-phenylisocyanato) thiophosphate and the like. If necessary, the isocyanates can be used in the form of so-called blocked isocyanates, ie, addition compounds with phenols, lactams, oximes and the like, which are diisocyanate dimers such as 1-methylbenzene-2,4-diisocyanate dimers, Or in the form of diisocyanate trimers such as isocyanurate, which can be used in the form of polyisocyanates obtained as adducts using any of a variety of polyols and the like. In addition, water-addition product isocyanates such as 2,4-toluene diisocyanate and diphenylmethane diisocyanate such as 1,3-bis (3-isocyanato-4-methylphenyl) urea; Polyol adducts such as trimethylolpropane adducts of toluene diisocyanate (trade names: Desmodule L and Coronate L); Phenol adducts isocyanates; Amine adducts isocyanates; And isocyanate compounds and isocyanate adduct compounds described in the specification of JP-A-10-76757 and in the specification of JP-A-10-95171.
    [518] The isocyanate compound is used in an amount of preferably 5 to 500 parts by weight, more preferably 20 to 200 parts by weight per 100 parts by weight of the colorless or pale dye dye precursor. When the proportion of the isocyanate compound is 5 parts by weight or more, a sufficient improvement effect of storage stability can be obtained, and the color development concentration is high. When the proportion of the isocyanate compound is 500 parts by weight or less, the isocyanate compound is rarely left in excess, which is preferable because it is economically advantageous.
    [519] By introducing an imino compound into the coloring composition of the present invention, storage stability is further improved.
    [520] Imino compounds that can be incorporated into the chromogenic composition of the present invention are colorless or light colored compounds having at least one imino group and which are solid at room temperature. Depending on the purpose, two or more imino compounds may be introduced in combination. As said imino compound, the compound described in JP-A-9-142032 can be mentioned and the content of the said reference is taken in here as a reference. Among the imino compounds described in the above reference, imino isoindolin derivatives are preferred, and 1,3-diimino-4,5,6,7-tetrachloroisoindolin, 3-imino-4,5,6 More preferred are, 7-tetrachloroisoindolin-1-one and 1,3-diimino-4,5,6,7-tetrabromoisoindolin.
    [521] The imino compound is used in an amount of preferably 5 to 500 parts by weight, more preferably 20 to 200 parts by weight, per 100 parts by weight of the colorless or pale dye dye precursor. When the ratio of the said imino compound is 5 weight part or more, the effect of improving storage stability is obtained. When the proportion of the imino compound is 500 parts by weight or less, the imino compound is rarely left in excess, which is preferable because it is economically advantageous.
    [522] In addition, by introducing an amino compound into the color-forming composition of the present invention, the storage properties of the original recording material surface and the printing portion are improved. Amino compounds that can be introduced are colorless or pale materials having one or more primary, secondary or tertiary amino groups. As said amino compound, the compound described in JP-A-9-142032 can be mentioned. Among the amino compounds described in the above references, particular preference is given to aniline derivatives having at least one amino group and represented by the formula:
    [523] [Formula Ⅷ]
    [524]
    [525] [Wherein, R 1 , R 2 , R 3 and R 4 are independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an amino group,
    [526] X 1 and X 2 are independently amino groups or represented by the formula b:
    [527] [Formula b]
    [528] ;
    [529] Y 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO- and -CONH- (wherein n is 1 or 2), and the following Chemical Formula a Is a group selected from the group consisting of any group represented by:
    [530] [Formula a]
    [531] ].
    [532] The amino compounds can be used alone or as mixtures thereof. In order to improve print preservation in plasticizer resistance, the proportion of the amino compound is preferably 1 to 500 parts by weight per 100 parts by weight of the colorless or pale dye precursor. If the content of the amino compound is 1 part by weight or more per 1 part of urea-urethane compound, print preservation can be improved. If the content is 500 parts by weight or less, since the performance characteristics of the obtained composition can be sufficiently improved, the above content is advantageous in terms of cost.
    [533] In addition, by introducing an acidic developing agent into the color developing composition of the present invention, sensitivity can be improved and a color tone can be provided to the color developing composition.
    [534] When the coloring composition of the present invention is used in a thermal recording material, as the acidic developer used, a conventional electron-accepting substance is used, and in particular, a phenol derivative; Aromatic carboxylic acid derivatives or metal compounds thereof; Salicylic acid derivatives or metal salts thereof; N, N-diaryl thiourea derivatives; Sulfonylurea derivatives and the like are preferred. Phenol derivatives are particularly preferred. Specific examples of the phenol derivatives include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (hydroxyphenyl) butane, 2,2-bis (hydroxyphenyl) pentane, 2,2-bis ( Hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl ) Sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, 4-hydroxyphenyl-4'-methylphenyl sulfone, 3-chloro-4-hydroxyphenyl-4'-methylphenyl sulfone, 3,4-di Hydroxyphenyl-4'-methylphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, bis (2-allyl-4-hydroxyphenyl ) Sulfone, 4-hydroxyphenyl-4'-benzyloxyphenyl sulfone, 4-isopropylphenyl-4'-hydroxyphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sulfone Feed, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, (4'-chlorobenzyl) 4-hydroxybenzoate, ethyl 1,2-bis (4'-hydroxybenzoate), pentyl 1,5-bis (4'-hydroxybenzoate), hexyl 1,6-bis (4'-hydrate Hydroxybenzoate), dimethyl 3-hydroxy phthalate, stearyl gallate, lauryl gallate and the like. Salicylic acid derivatives are 4-n-octyloxysalicylic acid, 4-n-butyloxysalicylic acid, 4-n-pentyloxysalicylic acid, 3-n-dodecyloxysalicylic acid, 3-n-octanoyloxysalicylic acid, 4-n- Octyloxycarbonylaminosalicylic acid, 4-n-octanoyloxycarbonylaminosalicylic acid, and the like. Sulfonylurea derivatives are, for example, compounds containing one or more arylsulfonylaminoureido groups, such as 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (o-toluenesulfonylaminocarbonylamino) diphenylmethane, 4,4-bis (p-toluenesulfonylaminocarbonylamino) diphenyl sulfide, 4,4-bis (p-toluenesulfonylaminocarbonyl Amino) diphenyl ether, N- (p-toluenesulfonyl) -N'-phenylurea and the like. Also, for example, 4,4 '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol, and mixtures composed mainly of the above compounds can also be used (e.g. D-90 (trade name, Nippon Soda). Co., Ltd. manufacture)).
    [535] Among the acidic developer exemplified above, 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone, bis (3-allyl-4-hydroxyphenyl) sulfone , 2,4'-dihydroxydiphenyl sulfone and 4,4 '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol can improve sensitivity and provide vivid color tone This is possible because it makes it obtainable.
    [536] In order to improve fog and thermal responsiveness and the like, for example, N-stearyl-N '-(2-hydroxyphenyl) urea, N-stearyl-N'-(3-hydroxyphenyl) Urea, N-stearyl-N '-(4-hydroxyphenyl) urea, p-stearoylaminophenol, o-stearoylaminophenol, p-lauroylaminophenol, p-butyrylaminophenol, m-acetylaminophenol, o-acetylaminophenol, p-acetylaminophenol, o-butylaminocarbonylphenol, o-stearylaminocarbonylphenol, p-stearylaminocarbonylphenol, 1,1,3- Tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-ethylphenyl) butane, 1,1,3 -Tris (3,5-di-tert-butyl-4-hydroxyphenyl) butane, 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) propane, 1,2, 3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tris (3-phenyl-4-hydroxyphenyl) butane, 1,1,3-tris (3 -Cyclohexyl-4- Hydroxy-5-methylphenyl) butane, 1,1,3-tris (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane, 1,1,3-tetra (3-phenyl-4-hydroxyphenyl Propane, 1,1,3,3-tetra (3-cyclohexyl-4-hydroxy-6-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxy-6-methylphenyl) Phenolic compounds such as butane, 1,1-bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) butane and the like can be added.
    [537] The acidic developer is used in an amount of preferably 5 to 500 parts by weight, more preferably 20 to 200 parts by weight per 100 parts by weight of the colorless or pale dye dye precursor. When the proportion of the acidic developer is 5 parts by weight or more, the color of the dye precursor is sufficient and the color concentration is high.
    [538] When the ratio of the acidic developer is 500 parts by weight or less, the acidic developer is hardly remaining, which is preferable because it is economically advantageous.
    [539] In addition, when the color development composition of the present invention is used for a pressure-sensitive recording material, the color development concentration can be improved by introducing an acidic developing agent into the color development composition, and a vivid color tone can be provided to the pressure-sensitive recording material.
    [540] In addition, as the acidic developer, an electron accepting material is used. The acidic developer may include, for example, inorganic compounds such as acidic clay, activated clay, attapulgite, bentonite, zeolite, colloidal silica, magnesium silicate, talc, aluminum silicate and the like; Phenol, cresol, butylphenol, octylphenol, phenylphenol, chlorophenol, salicylic acid and the like, or aldehyde condensed novolac resins derived therefrom and metal salts thereof; And 3-isopropylsalicylic acid, 3-phenylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-di-t-butylsalicylic acid, 3,5-di (α-methylbenzyl) salicylic acid, 3,5-di-t- Salicylic acid derivatives such as octylsalicylic acid, 3-methyl-5-benzylsalicylic acid, 3,5-di (α, α-dimethylbenzyl) salicylic acid, 3-phenyl-5- (α, α-dimethylbenzyl) salicylic acid, and metal salts thereof It includes.
    [541] In addition, the whiteness is improved by introducing a fluorescent dye into the coloring composition of the present invention. As the fluorescent dye to be introduced into the coloring composition of the present invention, various known dyes can be used, and stilbene derivatives, coumarin derivatives, pyrazoline derivatives, bisstyrylbiphenyl derivatives, naphthalimide derivatives, bisbenzoxazolyl derivatives, etc. May be mentioned. Fluorescent dyes are not limited to these, but diaminostilbendisulfonic acid derivatives are particularly preferred.
    [542] Regarding the amount of fluorescent dye used, the fluorescent dye is prepared to be present in an amount of preferably 0.01 to 3% by weight, more preferably 0.1 to 2% by weight, based on the total weight (solid form) of the chromophoric composition. If the amount of fluorescent dye used is greater than 3% by weight, the above chromophoric composition is in some cases colored. If the amount is less than 0.01% by weight, the effect of the fluorescent dye on the whiteness is lowered.
    [543] The coloring composition of the present invention may then contain a storage stability imparting agent. Preservative stability giving agents usable in the present invention are additives such as image stabilizers, light stabilizers, antioxidants.
    [544] By using the storage stability imparting agent in combination with a urea-urethane compound developer (i.e., a developer containing a urea-urethane compound) and a colorless and pale dye precursor, the light resistance of the color developing composition can be improved, and the light resistance This excellent recording material can be obtained.
    [545] Image stabilizers, which are preferred examples of storage stability imparting agents used in the present invention, are, for example, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1, 1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, hindered phenolic compound [eg 4,4'-butylidenebis (2-tert-butyl-5-methylphenol ), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-tert-butyl-5-methylphenol) and 2,2'-methylenebis ( 6-tert-butyl-5-methylphenol)], 4-benzyloxy-4 '-(2-methylglycidyloxy) diphenyl sulfone, 4,4'- diglycidyloxy-diphenyl sulfone, 1 , 4-diglycidyloxybenzene, sodium 2,2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, 2-propanol derivatives and salicylic acid derivatives. Typically, the image stabilizer is used in a ratio of preferably 100 to 500 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of a colorless or pale dye dye precursor. When the ratio of the image stabilizer is 5 parts by weight or more, light resistance is good and color development density is high. If the proportion of the image stabilizer is more than 1000 parts by weight, their light resistance is no longer enhanced, and the ratio is economically disadvantageous.
    [546] The light stabilizer as a preferable example of the storage safety imparting agent used in the present invention is, for example, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-t -Butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-t-butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1, 1,3,3-tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-t-butyl-2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 '-t-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3' , 5'-di-t-pentyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-t-butyl-2'-hydroxy-5'-octyloxycarbonylethylphenyl) -5- Chlorobenzotriazole and the like; 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- , 2'-hydroxy-4,4'-dimethoxy- or 4- (2-ethylhexyloxy) -2-hydroxybenzophenone derivative; 4-t-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylesorcinol, bis (4-t-butylbenzoyl) resorcinol, 2,4-di-t- Butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-t-butyl-4-hydroxybenzoate and the like; Ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxy-cinnamate, methyl α-cyano-β-methyl -p-methoxycinnamate and the like; Bis (2,2,6,6-tetramethyl-4-piperidyl) sevacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) adipate and the like; 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxyoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-t-butyloxanilide, 2 , 2'-di-dodecyloxy-5,5'-di-t-butyloxanide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) Oxanide, 2-ethoxy-5-t-butyl-2'-ethoxyoxanide, and the like; And 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5 -Triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl-6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4 -Dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, etc. Typically, the light stabilizer is 100 wt% of a colorless or pale dye dye precursor. It is preferably used in an amount of 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, and when the ratio of the light stabilizer is 5 parts by weight or more, the light resistance is good and the color development concentration is high. When the ratio of is more than 1000 parts by weight, their light resistance is no longer enhanced, and the ratio is economically disadvantageous.
    [547] As a preferred example of the storage safety imparting agent used in the present invention, the antioxidant is, for example, 2,6-di-t-butyl-4-methylphenol, 2-t-4,6-dimethylphenol, 2,6 -Di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dish Clopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2 , 6-dinononyl-4-methylphenol, 2,6-di-t-butyl-4-methoxymethylphenol, 2,4-dimethyl-6- (1'-methyl-undeca-1'-yl) Phenol, 2,4-dimethyl-6- (1'-methyl-heptadeca-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyl-trideca-1'-yl) phenol, And mixtures thereof; 2,4-di-octylthiomethyl-6-t-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6 -Di-dodecylthiomethyl-4-nonylphenol, and mixtures thereof; 2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, 2,6-diphenyl-4-octadecyloxy Phenol, 2,6-di-t-butylhydroquinone, 2,5-di-t-butyl-4-hydroxyanisole, 3,5-di-t-butyl-4-hydroxyanisole, 3,5 Di-t-butyl-4-hydroxyphenyl stearate, bis (3,5-di-t-butyl-4-hydroxyphenyl) adipate, and mixtures thereof; 2,4-bis-octylmercapto-6- (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6- Bis (3,5-di-t-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-t-butyl 4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3 , 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-t-butyl-4-hydroxy Phenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-tri Azine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate and the like; 2,2'-methylenebis (6-t-butyl-4-methylphenol), 2,2'-methylenebis (6-t-butyl-4-ethylphenol), 2,2'-ethylidenebis (4 , 6-di-t-butylphenol), 2,2'-ethylidenebis (6-t-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6-di-t-butyl Phenol), 4,4'-methylenebis (6-t-butyl-2-methylphenol), 1,1-bis (5-t-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [ 3,3'-bis (3'-t-butyl-4'-hydroxyphenyl) butyrate]; 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-t-butyl- 4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) phenol and the like. Typically, the antioxidant is used in an amount of preferably 5 to 1000 parts by weight, more preferably 10 to 500 parts by weight, per 100 parts by weight of the colorless or pale dye precursor. When the ratio of the antioxidant is 5 parts by weight or more, the light resistance is good and the color development concentration is high. If the ratio of antioxidants is more than 1000 parts by weight, their light resistance is no longer enhanced, and the ratio is economically disadvantageous.
    [548] The color developing composition of the present invention may be made of a recording material by forming a color developing layer of the composition by a method such as coating on some support. The structure of the recording material is variable depending on the type of recording material.
    [549] The color development composition of the present invention can be used for any of various recording materials such as a thermal recording material, a reduced pressure recording material, and the like, and is particularly suitable for a thermal recording material.
    [550] When the color developing composition is used for the thermosensitive recording material, a thermosensitive recording layer is formed on the support, which can be colored when heated. Specifically, the above-mentioned colorless or light-colored dye precursors such as the urea-urethane compound, leuco dye, and the like, and the heat-soluble material described below are applied to the support together with other necessary components in the form of dispersion, respectively, to provide a thermal recording layer. It needs to be formed. The dispersion is prepared by finely pulverizing at least one compound, which is each component described above, in an aqueous solution containing a compound having a dispersing ability, such as a water-soluble polymer, a surfactant, or the like using a sand grinder. The particle diameter of each of the dispersions obtained is preferably adjusted to 0.1 to 10 mu m, especially about 1 mu m. Specific examples of compounds having a dispersing ability that can be used in the present invention include poly (vinyl alcohol), carboxylic acid-modified poly (vinyl alcohol), sulfonic acid-modified poly (vinyl alcohol), methyl cellulose, hydroxypropylmethyl cellulose Water-soluble polymers such as hydroxypropyl cellulose and the like; Condensed naphthalenesulfonates, polyoxyethylene alkyl ether sulfate ester salts (eg sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene phenyl ether sulfate), dialkylsulfo succinic ester Anionic surfactants such as sodium, alkylphosphates (eg, diethanolamine alkylphosphates and potassium alkylphosphates), special carboxylic acid-based polymers, and the like; Nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, polyethylene glycol fatty acid esters and the like; And cationic surfactants such as dicyanamidopolyamine, tertiary amine salts, quaternary amine salts, and the like can be used. Of these, polyvinyl alcohol, carboxylic acid-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and methyl cellulose are particularly preferred. The compounds exemplified above can be used alone or as mixtures.
    [551] When the urea-urethane compound developer according to the present invention is used in a thermosensitive recording material, the average particle size of the urea-urethane compound developer is adjusted to 0.05 µm or more and 5 µm or less, thereby having sufficient color sensitivity and developing a printed image. It is possible to obtain this thermally stable recording material which is very stable and has good plasticizer resistance. It is more preferable that the average particle size is 0.1 µm or more and 3 µm or less. If the average particle size is less than 0.05 mu m, the preservation of the original recording material surface for the plasticizer is lowered. On the other hand, if the average particle size is more than 5 mu m, the sensitivity of the thermal recording material is reduced.
    [552] In particular, when wet pulverizing the urea-urethane compound in an aqueous medium, the temperature of the aqueous medium is preferably 60 ° C. or less. At the time of grinding, the urea-urethane compound developer is in contact with water, so that hydrolysis of its urethane group proceeds depending on the conditions. Therefore, the sensitivity of the thermal recording material obtained using the urea-urethane compound developer tends to be decreased. In particular, when the medium temperature at the time of grinding | pulverization is more than 60 degreeC, a sensitivity will fall significantly. It is more preferable that the said temperature at the time of grinding | pulverization is 40 degrees C or less.
    [553] In addition, when the urea-urethane compound developer is pulverized, it is preferable to pulverize in the neutral pH range of 5 to 10. When the pH at the time of grinding | pulverization is less than 5, since an inorganic pigment etc. decompose at the time of manufacture of a thermal coating liquid, there exists a tendency for a sensitivity to decrease. On the other hand, when the pH is greater than 10, the urea-urethane compound developer is hydrolyzed, so in some cases the sensitivity is reduced. Specific examples of the dispersants usable for preparing the dispersion of the urea-urethane compound developer by grinding in the present invention include poly (vinyl alcohol), carboxylic acid-modified poly (vinyl alcohol), sulfonic acid-modified poly (vinyl alcohol) Water-soluble polymers such as methyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose and the like; Condensed naphthalenesulfonates, polyethylene alkyl ether sulfate ester salts (eg, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate and sodium polyoxyethylene phenyl ether sulfate), dialkylsulfo succinic ester sodium, Anionic surfactants such as alkyl phosphates (eg, diethanolamine alkyl phosphate and potassium alkyl phosphate), special carboxylic acid-based polymers and the like; Nonionic surfactants such as polyoxyethylene alkyl phenylether, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, polyethylene glycol fatty acid esters and the like; And cationic surfactants such as dicyanamidopolyamine, tertiary amine salts, quaternary ammonium salts, and the like. Among them, the water-soluble polymer and the anionic surfactant have high sensitivity irrespective of the dispersion conditions of the urea-urethane compound developer, and the preservation of the surface of the original recording material for the plasticizer regardless of the average particle size of the urea-urethane compound. It is particularly preferable because it makes it possible to obtain an improved thermal recording material. Poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, polycarboxylic acid ammonium salt, water soluble low molecular weight copolymer and sodium 2-ethylhexylsulfosuccinate More preferred. Among these, methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate and water-soluble low molecular weight copolymers are more preferable, and hydroxypropylmethyl cellulose is most preferred. The dispersants exemplified above can be used alone or as mixtures thereof.
    [554] As dispersants usable in the present invention for preparing dispersions of colorless or pale dye dye precursors, the same compounds as those used as dispersants for the dispersion of the urea-urethane compound developer can be used. Among the above compounds, a water-soluble polymer, an anionic surfactant, and a mixed dispersant of the two kinds of compounds are particularly preferred for improving the sensitivity of the thermal recording material and the preservation of the original recording material surface to the plasticizer. More preferred are mixed dispersants consisting of methyl cellulose or hydroxypropylmethyl cellulose as the water soluble polymer, and polyoxyethylene alkyl ether sulfate or sodium 2-ethylhexylsulfosuccinate as the anionic surfactant. Most preferred is a mixed dispersant of hydroxypropylmethyl cellulose and sodium 2-ethylhexylsulfosuccinate.
    [555] It is preferable that the pH of the coating liquid containing the said urea-urethane compound and a colorless or pale dye precursor is 5-12.
    [556] In addition to the above components, the thermally sensitive recording layer includes diatomaceous earth, talc, kaolin, calcined kaolin, potassium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formaldehyde Pigments such as resins and the like. Further, the thermal recording layer may, if necessary, include metal salts of higher fatty acids such as zinc stearate, calcium stearate and the like; And waxes such as paraffin, paraffin oxide, polyethylene, polyethylene oxide, stearamide, caster wax, and the like, for example, may be used for the purpose of preventing abrasion and sticking of the head. If necessary, the thermal recording layer may also include a dispersant such as sodium dioctylsulfosuccinate and the like; Ultraviolet absorbers such as benzophenone series and benzotriazole series; Surfactants; Fluorescent dyes and the like.
    [557] As binders that can be used to form the thermal recording layer, for example, starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, poly (vinyl alcohol), modified poly (vinyl alcohol), sodium poly (acrylic) Water soluble binders such as acrylamide-acrylic acid ester copolymer, acrylamide-acrylic acid ester-methacrylic acid terpolymer, alkali salt of styrene-maleic anhydride copolymer, alkali salt of ethylene-maleic anhydride copolymer, and the like; And latex-based water-insoluble binders such as styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, methyl acrylate-butadiene copolymer and the like.
    [558] As the support for the thermal recording layer, paper is mainly used, but in addition to the paper, any of various woven fabrics, nonwoven fabrics, synthetic resin films, laminated papers, synthetic papers, metal foils, and composite sheets obtained by combining two or more kinds of the above according to the purpose Can be used. The basis weight of the support is preferably 40 g / m 2 to 200 g / m 2 . The support is preferably excellent in surface smoothness and flatness, since it is preferable that the thermal recording material obtained by using the support has as high planarity as possible. Therefore, it is preferable to surface-treat the support by applying heat and pressure using any mechanical calender, soft calender, supercalender, or the like.
    [559] The surface pH of the support is preferably 3 to 9, more preferably 5 to 9, most preferably 6 to 8. When the surface pH of the support is less than 3, fog tends to occur. If the pH of the support is greater than 12, the urea-urethane compound decomposes, so in some cases the color development concentration is reduced.
    [560] The thermal recording layer may be composed of a single layer or a plurality of layers. The thermal recording layer may have a multilayer structure formed by, for example, introducing each of the color development components into one layer. A protective layer composed of a single layer or a plurality of layers may be formed on the thermal recording layer, and an intermediate layer composed of a single layer or a plurality of layers may also be formed between the support and the thermal recording layer. The thermal recording layer can be obtained by mixing an aqueous dispersion prepared by finely pulverizing each color development component or any other components with a binder or the like, applying the obtained mixture onto a support, and then drying the mixture. It is preferable that the coating amount of the said coating liquid is 1-15 g / m <2> of coating liquid in a dry state.
    [561] When the color developing composition of the present invention is used in a thermosensitive recording material, a heat-fusible material can be introduced into the color developing composition to improve the sensitivity. It is preferable that a thermomeltable material is a substance which has a melting point of 60 degreeC-180 degreeC, especially the substance which has a melting point of 80 degreeC-140 degreeC. The heat-fusible materials are, for example, benzyl p-benzyloxybenzoate, stearamide or emulsification products thereof, palmiamide, N-methylolstearicamide, β-naphthyl benzyl ether, N-stearylurea, N , N'- distearylurea, phenyl β-naphthoate, phenyl-1-hydroxy-2-naphthoate, β-naphthol (p-methylbenzyl) ether, 1,4-dimethoxynaphthalene, 1- Methoxy-4-benzyloxynaphthalene, N-stearoylurea, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, 1-phenoxy-2- (4-chlorophenoxy) Ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate, m-terphenyl, dibenzyl oxalate and (p-chlorobenzyl) oxalate.
    [562] 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-difluorobenzophenone, diphenyl sulfone, 4,4'-dichlorodiphenyl sulfone, 4,4 ' -Difluorodiphenyl sulfone, 4,4'-dichlorodiphenyl disulfide, diphenylamine, 2-methyl-4-methoxydiphenylamine, N, N'-diphenyl-p-phenylenediamine, 1- ( N-phenylamino) naphthalene, benzyl, 1,3-diphenyl-1,3-propanedione and the like are very effective for improving the sensitivity, and therefore are preferable as the heat-soluble material.
    [563] As the heat-soluble material, benzyl 4-hydroxybenzoate, 4- (benzyloxy) phenol, 2,4-dihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 4 , 4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, Bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 3,4-dihydroxyphenyl-4'-methylphenyl sulfone, bis (2-methyl-3-tert-butyl-4-hydroxyphenyl) sul Feed, 4,4'-dihydroxydiphenyl ether, 4,4'-thiodiphenol, 4,4'-dihydroxydiphenylmethane, 3,3'-dihydroxydiphenylamine, bis (4 -Hydroxy-3-methylphenyl) sulfide, 4-hydroxy-4'-isopropoxydiphenyl sulfone, 4,4'-thiobisbenzenethiol, salicylicanilide, 4,4'-diamino-3, 3'-diethyldiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-dia Minodiphenylmethane, 4,4'-thiodinaniline , 2,2'-dithiodianiline, 4,4'-dithiodianiline, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylether, 3,4'-diaminodiphenyl Ether, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, bis (3-amino-4-chloro-phenyl) sulfone, bis (3,4-diaminophenyl) sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl methane, 4,4'-dia Minodiphenylamine, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, acetoacetic acid o-chloroanilide, acetoacetic acid anilide, acetoacetic acid o-toluidide, acetoacetic acid p-tolui Died, acetoacetic acid o-anisidide, acetoacetic acid m-xylide, p-acetotolideide and the like can be used.
    [564] Among them, diphenyl sulfone, di-p-methylbenzyl oxalate, benzyl, β-naphthyl benzyl ether, p-benzyl biphenyl, 1,2-di (m-methylphenoxy) ethane, 1,2-dipe Oxy-methylbenzene, m-terphenyl and stearamide are preferred for use.
    [565] Further, among the above-mentioned heat-fusible materials, the use of a heat-fusible material of the following formula (XVII) significantly improves the sensitivity of the recording material, the plasticizer resistance of the printing portion, and the heat resistance of the original recording material surface in the thermal recording material. effective. Particularly preferred is a heat-soluble material represented by the following general formula (XVII).
    [566] [Formula X ']
    [567]
    [568] [Wherein Y is -SO 2 -,-(S) n- , -O-, -CO-, -CH 2- , -CH (C 6 H 5 )-, -C (CH 3 ) 2- , -COCO-, -CO 3 -, -COCH 2 CO-, -COOCH 2 -, -CONH-, -OCH 2 - , and -NH- {wherein, n is 1 or 2} and either one of,
    [569] The hydrogen atom of each benzene ring is halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanate group, isothiocyanate group, mercapto group, sulfamoyl group, sulfone group, amino group, aromatic compound residue , An aliphatic compound residue or a heterocyclic compound residue.
    [570] [Formula X ']
    [571]
    [572] [Wherein, the hydrogen atom of each benzene ring is a halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanate group, isothiocyanate group, mercapto group, sulfamoyl group, sulfonic acid group, amino group , Aromatic compound residues, aliphatic compound residues or heterocyclic compound residues.
    [573] The above-mentioned heat-fusible materials can be used alone or as a mixture thereof. In order to achieve sufficient thermal responsiveness, the heat-fusible material is used in a proportion of preferably 100 to 300 parts by weight, more preferably 20 to 250 parts by weight, per 100 parts by weight of the colorless or pale dye precursor.
    [574] As the dispersant usable in the present invention for preparing the dispersion of the thermomeltable material by grinding, the same compound as used as the dispersant for the dispersion of the urea-urethane compound developer can be used. Among the above compounds, water-soluble polymers and anionic surfactants are particularly preferred in order to improve the preservation of the original recording material surface with respect to the plasticizer of the thermal recording material. Poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalene sulfonate, polycarboxylic acid ammonium salt, water soluble low molecular weight copolymer and sodium 2-ethylhexylsulfosuccinate More preferred. Among these, modified poly (vinyl alcohol), methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalene sulfonate, polycarboxylic acid ammonium salt are even more preferred, and hydroxypropylmethyl cellulose is most preferred. The dispersants exemplified above can be used alone or as mixtures thereof.
    [575] When the urea-urethane compound developer is pulverized, finely pulverizing (co-milling) the developer with the above-mentioned heat-fusible material is heat-sensitive as compared to mixing the pulverized compound after pulverizing each compound. The sensitivity of the recording material and the plasticizer resistance are further improved. The reason why this effect is obtained is not completely clear.
    [576] In addition, the moisture resistance of the non-printed portion (original surface) of the thermal recording material is one dispersant for the urea-urethane compound developer selected from methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalenesulfonate and a water-soluble low molecular weight copolymer. Or more, and by using at least one dispersant for the heat-soluble material selected from poly (vinyl alcohol), methyl cellulose, hydroxypropyl methyl cellulose, condensed sodium naphthalenesulfonate and polycarboxylic acid ammonium salts.
    [577] The color development composition of the present invention can be used in various thermal recording materials, and is particularly suitable for thermal magnetic recording materials, thermal recording labels, multicolor thermal recording materials and thermal recording materials for laser marking.
    [578] When the coloring composition of the present invention is used for a thermosensitive magnetic recording material, the recording material includes a thermosensitive recording layer containing a urea-urethane compound developer, on one side of the support, and a magnetic recording layer on the other side. It is preferably in form.
    [579] The magnetic recording layer of the thermosensitive magnetic recording material uniforms ferromagnetic powders such as barium ferrite, strontium ferrite, Co-γ-Fe 2 O 2 , γ-Fe 2 O 2 , and the like in an aqueous binder such as an aqueous emulsion resin. It is obtained by coating a support with a coating material prepared by dispersion, and drying the coated support. In this case, antistatic agents (such as carbon graphite), lubricants (such as waxes), color pigments for color adjustment, coating film softeners (such as poly (ethylene oxide)) and the like can be added according to their purpose. .
    [580] The thermal magnetic recording material of the present invention is suitable as a thermal magnetic recording material such as a train ticket, a ticket, or a prepaid card.
    [581] When the coloring composition of the present invention is used for a label for thermal recording, the label has a thermal recording layer containing a urea-urethane compound developer on one side of the support, and an adhesive layer on the other side. It is preferably in form.
    [582] The pressure-sensitive adhesive layer of the thermal recording material is mainly composed of a pressure-sensitive adhesive. The said pressure sensitive adhesive contains a synthetic rubber base emulsion type adhesive, an acrylic emulsion type adhesive, a natural rubber base solvent type adhesive, and a silicone base solvent type adhesive. Among these, an acrylic emulsion type adhesive is especially preferable.
    [583] If necessary, in the heat-sensitive recording label produced by the method according to the present invention, a reverse-side layer (back coating layer) is formed between the adhesive layer and the support, and the curl of the heat-sensitive recording label ( curl) calibration, antistatic and friction coefficient adjustment are possible. As the coating liquid component for the back layer, the coating method of the coating liquid, and the like, the same components, methods, and the like as in the formation of the thermal recording layer can be used. The dry coating amount of the coating solution is preferably in the range of 0.2 to 10.0 g / m 2 .
    [584] The coating order is not particularly limited in the manufacture of the label for thermal recording. For example, one of the following sequences can be used:
    [585] Forming a thermal recording layer on one side of the support, followed by forming a back coating layer on the other side, and then forming an adhesive layer on the back coating layer; or
    [586] A back coating layer is formed on one side of the support, and then a thermal recording layer is formed on the other side, and then an adhesive layer is formed on the back coating layer.
    [587] Regarding the method for forming the adhesive layer on the back coating layer, the liquid for forming the adhesive layer is directly applied on the back coating layer and dried, or the liquid for forming the adhesive layer is previously applied on the release paper, Subsequently, the material obtained by drying can be attached to the back coating layer side of the thermal recording material in which no adhesive layer is formed.
    [588] In addition, thermal response can be improved by forming an intermediate layer composed of a single layer or a plurality of layers between the thermal recording layer and the support. The intermediate layer consists mainly of organic or inorganic pigments, hollow particles, and aqueous binders such as water soluble polymers or latexes. As the organic or inorganic pigments and the aqueous binder, the same organic or inorganic pigments and aqueous binders as used in the above-mentioned thermal recording layer can be used. The method for forming the intermediate layer is not particularly limited. As the above method, the same method as that for forming the heating recording layer can be employed. The dry coating amount for forming the interlayer is preferably 2.0 to 15.0 g / m 2 .
    [589] When the coloring composition of the present invention is used for a multicolored thermosensitive recording material, the recording material includes two or more thermosensitive recording layers formed on one side of the support, and the at least one thermosensitive recording layer contains a urea-urethane compound developer. It is preferably in form.
    [590] As the support used, the polyolefin resin and the white inorganic pigment are kneaded by heat, the kneaded product is extruded through a die, the extruded product is stretched in the longitudinal direction, and the film made of the polyolefin resin and the white inorganic pigment is drawn. Synthetic paper prepared by laminating in one or two layers on each side of the finished product and stretching the resulting assembly in a transverse direction to make it translucent or opaque; One or two or more mixtures of thermoplastic resins such as polyethylene, polypropylene, ethylene vinyl acetate copolymer resin, poly (vinyl chloride), polystyrene, polyester and the like are kneaded by heat, and the extruded product is then extruded through a die A film obtained by biaxially stretching an extruded product; An opaque film obtained by mixing a white inorganic pigment with any of the resins exemplified above, followed by biaxial stretching; And supports made from pulp fibers such as woodfree paper, medium-duty paper, machine glazed paper, recycled paper, coated paper and the like. The support made of pulp fibers is preferably formed with a heat-sensitive layer after the coating layer is formed in advance in order to improve the uniformity of the image.
    [591] The thermochromic layer according to the present invention contains, as main components, a color developing composition and an adhesive capable of causing a color reaction resulting from mutual contact of materials by heating. Specific examples of the chromophoric composition include a combination of the urea-urethane developer and the colorless or pale dye precursor which can color the dye precursor upon heating; And a combination of a diazo compound and a coupler that can be developed by reaction with the diazo compound. If desired, crosslinking agents, pigments and heat-fusible materials can be introduced into the color development composition. Usually, it is preferable that the coating amount of the said thermochromic color providing layer is 3-15 g / m <2> from a viewpoint of color development sensitivity and color development density.
    [592] As the coloring dye, a colorless or pale dye precursor as described above, which is capable of coloring, is used when reacting with a urea-urethane compound developer by heating.
    [593] On the other hand, in a thermal recording layer containing, as a main component, a diazo compound and a coupler capable of developing color by reaction with the diazo compound, the compound reacts with a well known photodegradable diazo compound and the diazo compound. It is a coupler capable of forming a pigment. If necessary, a basic substance or the like may be added to promote the reaction of the diazo compound with the coupler. The coupler and the basic material are mixtures thereof, and are preferably used at a ratio of 10 to 1000 parts by weight and 10 to 2000 parts by weight, respectively, per 100 parts by weight of the diazo compound.
    [594] The term "photodegradable diazo compound" as used herein refers to a pigment by reaction with a coupling component upon heating, such as a diazonium salt, a diazosulfonate compound, a diazoamino compound, a quinonediazide compound, or the like. It means the diazo-type photosensitive material which can be formed. The diazonium salt relates to a compound represented by the following formula:
    [595] Ar-N 2 + and X -
    [596] -, Ar is the aromatic part of the formula, N + 2 is a diazonium group, X - is an anion pair.
    [597] The compound has various maximum absorption wavelengths depending on the position and type of the substituent of the Ar moiety.
    [598] Specific examples of the diazonium compound used in the present invention are 4-dimethylaminobenzenediazonium, 4-diethylaminobenzenediazonium, 4-dipropylaminobenzenediazonium, 4-methylbenzylaminobenzenediazonium, 4-di Benzylaminobenzenediazonium, 4-ethylhydroxyethylaminobenzenediazonium, 4-diethylamino-2-methoxybenzenediazonium, 4-dimethyl-3-methylbenzenediazonium, 4-benzoylamino-2,5 Diethoxybenzenediazonium, 4-morpholinobenzenediazonium, 4-morpholino-2,5-diethoxybenzenediazonium, 4-morpholino-2,5-dibutoxybenzenediazonium, 4- Anilinobenzenediazonium, 4-toluylmercapto-2,5-diethoxybenzenediazonium, 4- (N, N-dioctylcarbamoyl) benzenediazonium, 2-octadecyloxybenzenediazonium, 4 -(4-tert-octylphenoxy) benzenediazonium, 4- (2,4-di-tert-amylphenoxy) benzenediazonium, 2- (4-tert-octylphenoxy) benzenediazonium, 5- Chloro-2- (4-tert-octylphenoxy) benzene Azo titanium, 2,5-bis-a, etc. octadecyloxyphenol benzene diazonium, 4- (N- octyl-lauroyl amino) benzene diazonium-octadecyloxyphenol benzene diazonium, 2,4-bis. Specific examples of the diazonium salt paired anion used in the present invention is Cl and 1 / 2Z n Cl 2 -, BF 4 -, PF 6 -, B (ph) 4 -, C n F 2n + 1 COO - (n is 3 to 9), C m F 2m + 1 SO 3 − (m is 2 to 8), (C k F 2k + 1 SO 2 ) 2 CH − (k is 1 to 18), and the like.
    [599] Diazosulfonate compounds used in the present invention are compounds represented by the formula:
    [600] Ar-N 2 -SO 3 Na
    [601] [Wherein Ar is an aromatic moiety].
    [602] Specific examples of the diazo sulfonate compound used in the present invention are 2-methoxy, 2-phenoxy, 2-methoxy-4-phenoxy, 2,4-dimethoxy, 2-methyl-4-methoxy Methoxy, 2,4-dimethyl, 2,4,6-trimethyl, 2,4,6-trimethoxy, 2,4-dimethoxy-5-chloro, 2-methoxy-5-nitro, 2-methoxy -5-acetamido, 2-methoxy-5-N, N-diethylsulfonamido, 2-methoxy-5-N-phenylcarbamyl, 3-methyl, 4-methyl, 4-methoxy, Sodium benzenediazosulfonate with one or more substituents including 4-ethoxy, 4-phenyl, 4-phenoxy, 4-acetamido and the like; And 4- (N-ethyl-N-benzylamino), 4- (N, N-dimethylamino), 4- (N, N-diethylamino), 4- (N, N-diethylamino) -3 -Chloro, 4- (N-ethylamino) -3-methyl, 4- (N, N-diethylamino) -2-methyl, 4- (N-ethyl-N-β-hydroxyethylamino), 4 -Pyrrolidino-3-chloro, 4-pyrrolidino-3,5-dichloro, 4-morpholino, 4-morpholino-3-chloro, 4-morpholino-2-methoxy, 4- Morpholino-2,5-diethoxy, 4-morpholino-2,5-dibutoxy, 4- (4'-tolylmercapto) -2,5-dibutoxy, 4- (4'-tolylmer Sodium benzenediazosulfonate having one or more substituents including capto) -2,5-diethoxy, 4- (4'-methoxybenzoylamino) -2,5-dibutoxy, 4-diphenylamino and the like . When any of the above diazosulfonate compounds is used, the diazosulfonate compound is preferably activated by light irradiation before printing.
    [603] Diazoamino compounds usable in the present invention are compounds obtained by coupling a diazo group to dicyandiamide, sarcosine, methyltaurine, N-ethylanthranilic acid-5-sulfonic acid, monoethanolamine, diethanolamine, guanidine and the like. to be.
    [604] The quinonediazide used in the present invention is regarded as an internal salt type diazonium salt in terms of structure, and is, for example, o-quinonediazide or o-naphthoquinonediazide. The quinonediazides are salts, esters, such as 1,2-quinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid and the like; Amide compounds. Specific examples of the quinonediazide used in the present invention include sodium 1,2-quinonediazide-4-sulfonate, sodium 1,2-naphthoquinonediazide-5-sulfonate, sodium 1,2-naphtho Quinonediazide-4-sulfonate, p-cumylphenyl 1,2-naphthoquinonediazide-5-sulfonate, p-cumylphenyl 1,2-naphthoquinonediazide-4-sulfonate, methyl 1, 2-naphthoquinone diazide 5-sulfonate, ethyl 1,2-naphthoquinone diazide 5-sulfonate, 1,2-naphthoquinone diazide-5-sulfonic acid dimethylamide, 1,2-naphthoquinone Esters of diazide-5-sulfonic acid and novolak resins. In addition, the photodegradable diazo compound may be used alone or in combination.
    [605] The coupler used in the present invention is to react with the diazo compound to form a pigment. For example, a typical coupler capable of forming a yellow pigment has a methylene group which is activated by a carbonyl group adjacent thereto, wherein RCOCH 2 CO-R 'wherein R is an alkyl group or an allyl group, and R' Is an aromatic amine]. Magenta couplers are, for example, 1) cyanoacetyl derivatives of cyclic compounds, or 2) heterocyclic compounds with active methylene or any other coupling moiety on a heterocyclic ring. Magenta couplers include, for example, pyrazolone compounds and indazolone compounds. Cyan couplers include, for example, phenol and naphthol.
    [606] Specific examples of couplers used in the present invention are 4- (p-toluenesulfonylamino) -ω-benzoylacetanilide, α-benzoyl-o-methoxyacetanilide, 2-cyanoacetyl-coumarone, 1- ( 2,4,6-trichlorophenyl) -3-p-nitroamino-2-pyrazol-5-one, resorcin, phloroglucin, 2,3-dihydroxynaphthalene, 2, 6-dibromo-1,5-dihydroxynaphthalene, N- (o-acetamidophenethyl) -1-hydroxy-2-naphthoamide, and the like. In addition, the coupler may be used alone or in combination.
    [607] In order to proceed more smoothly the coupling reaction between the diazo compound and the coupler under a basic atmosphere, it is preferable that a basic substance is introduced into the thermochromic layer. As the basic substance, a slightly water-soluble or water-insoluble basic substance, or a substance capable of generating alkali upon heating is used. The basic substances are, for example, inorganic and organic ammonium salts, organic amines, amides, ureas and thioureas and derivatives thereof, thioazoles, pyrroles, pyrimidines, piperazine, guanidines, imidazoles, imidazolines, triazoles, Nitrogen-containing compounds such as morpholine, piperidine, amidine, formamidine, pyridine and the like.
    [608] Specific examples of the compound include tricyclohexylamine, tribenzylamine, octadodecylbenzylamine, stearylamine, allylurea, thiourea, methylthiourea, allylthiourea, ethylenethiourea, 2-benzylimidazole, 4-phenylimidazole, 2-phenyl-4-methylimidazole, 2-undecylimidazoline, 2,4,5-trifuryl-2-imidazoline, 1,2-diphenyl-4, 4-dimethyl-2-imidazoline, 2-phenyl-2-imidazoline, 1,2,3-triphenylguanidine, 1,2-dicyclohexylguanidine, 1,2,3-tricyclohexylguanidine, Guanidine trichloroacetate, N, N'-dibenzylpiperazine, 4,4'-dithiomorpholine, morpholinium trichloroacetate, 2-aminobenzothiazole, 2-benzoylhydrazinobenzothiazole and the like. The basic materials may be used alone or in combination.
    [609] In the present invention, the storage stability can be improved by adding a weakly acidic material such as citric acid, tartaric acid, oxalic acid, boric acid, phosphoric acid, pyrophosphoric acid, and the like to the thermochromic layer formed by the combination of a diazo compound and a coupler.
    [610] Needless to say, the color development component used in the present invention can be used in a state of solid dispersion achieved by dispersing the component in an aqueous solution of a water-soluble polymer, and then applying and drying, as in the usual method employed for the thermal recording material. have. In addition, as described in JP-A-59-190886, JP-A-60-49991, JP-A-61-169281 and the like, the color-coating agent is microencapsulated, and the color-coating agent and the developer at room temperature can be utilized by the isolation effect of the capsule wall. It is possible to improve the raw preservation property by preventing contact. The microcapsules are characterized in that the coloring agent and the developer can be brought into contact with each other only during heating above a certain temperature. The onset temperature of the contact of the color developer with the developer can be controlled by suitably selecting the material of the capsule wall, the core material of the capsule, additives and the like.
    [611] As the material of the microcapsule wall of the present invention, for example, polyurethane, polyurea, polyester, polycarbonate, urea-formaldehyde resin, melamine resin, polystyrene, styrene-methacrylate copolymer, gelatin, poly (vinyl) Mention is made of conventional microcapsule wall materials such as pyrrolidone), poly (vinyl alcohol) and the like. The polymers may be used alone or in combination.
    [612] In the present invention, as the pressure-sensitive adhesive contained in the thermochromic layer, a water-soluble resin or a water-dispersible resin can be used. However, when any of the above resins are mixed with the respective dispersions of the color developing dye and the developer, the obtained mixture needs not to be colored, aggregated or high in viscosity. In addition, the coating film formed as the thermal recording layer needs to be strong and does not need to have a sensitivity reducing effect. The content of the pressure-sensitive adhesive in the heat-sensitive color developing layer is preferably 8 to 20% based on the amount (solid form) of the heat-sensitive color developing layer. A content of less than 8% is disadvantageous in that the strength of the coating film is low. Contents above 20% cause a problem of desensitization. In order to improve the water resistance of the thermal coloring layer, a crosslinking agent for curing a resin can be used.
    [613] In the multicolored thermosensitive recording material of the present invention, forming an intermediate layer between the thermosensitive recording layers is effective in improving heat distribution. The intermediate layer contains the same resin as the water-soluble or water-dispersible resin used as the adhesive in the thermal recording layer as its main constituent, and may further contain a pigment, a crosslinking agent and the like. The coating amount of the intermediate layer is preferably 0.1 to 5.0 g / m 2 . If the coating amount is less than 1.0 g / m 2 , the effect of preventing diffusion between recording layers is not sufficient, which causes a deterioration in image quality. If the coating amount is greater than 5.0 g / m 2 , there is a disadvantage that the sensitivity is lowered.
    [614] As a particularly preferred embodiment of the multicolored thermosensitive recording material of the present invention, two thermally sensitive recording layers each having a different color development temperature and a different color tone are formed on one side of the support, and are formed by laminating an upper layer among the recording layers. The multicolored thermosensitive recording material characterized in that it contains an agent used as both a color developer and a color reducing agent, or a reversible developer, and the lower layer of the thermosensitive recording layer contains a urea-urethane compound developer. Can be.
    [615] Among them, the agent used as both a color developer and a color reducer in the upper thermal recording layer is an amphoteric compound having an acidic group having a color developing function and a basic group having a color fading function, which performs a color developing function at low temperature heating, Performs the bleaching function when heated. Representative examples of acidic groups are phenolic hydroxyl groups or carboxyl groups. Representative examples of basic groups are amino groups. The amphoteric compound may have a basic group as a functional group, but it is preferred to have a basic group as part of a salt compound, such as in a complex of a phenolcarboxylic acid compound and an amine compound. Specific examples of the formulations used as both developer and color reducer are as follows. Phenolic carboxylic acid compounds constituting the formulations used as both developer and colorant include 2-hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5- Dihydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, gallic acid, bis (4 -Hydroxyphenyl) acetic acid, 3,3-bis (4-hydroxyphenyl) propionic acid, and the like.
    [616] The amine compound which forms a salt or a complex salt with a phenolcarboxylic acid compound is octylamine, nonylamine, decylamine, laurylamine, tetradecylamine, heptadecylamine, stearylamine, behenylamine, 3-meth Methoxypropylamine, hexamethylenediamine, and the like.
    [617] The reversible developer is, for example, a phenolic compound or phosphonic acid compound having an aliphatic hydrocarbon group having 8 or more carbon atoms. Specific examples of the reversible developer are those mentioned below. The reversible developer is not limited to those mentioned below, and any reversible developer can be used as long as it performs a color developing function at low temperature heating and a bleaching function at high temperature heating.
    [618] The reversible developer is 4- (octadecylthio) phenol, 4- (docosylthio) phenol, 4- (octadecyloxy) phenol, 4- (docosyloxy) phenol, N-octadecyl-4-hydride Oxybenzamide, 4'-hydroxydocoic acid anilide, N- (4-hydroxyphenyl) -N'-n-octadecylurea, docosylphosphonic acid, and the like. By using the multicolored thermosensitive recording material of the present invention, when performing recording using a thermal printer or the like, printing by low temperature heating only develops a low temperature color developing layer, and printing by high temperature heating bleaches the low temperature color developing layer of the printing portion. And only the high temperature color developing layer is developed.
    [619] The urea-urethane compound can be used to obtain an article for laser marking with sufficient color development, and to obtain a very stable colored printed image in which the image is almost not discolored or faded even by fats and oils, drugs, fingerprints and the like. Therefore, the above use is particularly advantageous in view of long time storage of the recording.
    [620] It is preferable that the thermal recording layer of the laser marking article of this invention contains a recording sensitivity improving agent.
    [621] As the recording sensitivity improving agent available there, a compound capable of absorbing the laser beam used for irradiation is used. Specific examples thereof include aluminum hydroxide, wollastonite, bentonite, mica (such as mica and gold mica), calcium silicate, talc, kaolin, clay and silicate minerals (such as foyaite, hornblende and Various inorganic compounds such as albite). Particular preference is given to aluminum hydroxide, dolomite, wollastonite and kaolin. These inorganic compounds may be used alone or as a mixture thereof.
    [622] The ratio of the colorless or pale dye precursor and the recording sensitivity improving agent used in the thermal recording material of the present invention is not particularly limited, and may be appropriately selected depending on the type of the dye precursor and the recording sensitivity improving agent used. Typically, the recording sensitivity improving agent can be used in a ratio of 10 to 5000 parts by weight, preferably 100 to 2000 parts by weight, per 100 parts by weight of the color developer.
    [623] The content of the dye precursor, the urea-urethane compound developer and the recording sensitivity enhancer in the thermal recording layer can be adjusted as follows: Based on the total weight (solid form) of the layer, the content of the dye precursor is 5 to 30 weight. %, Preferably in the range of 10 to 25% by weight, the content of the urea-urethane compound developer is in the range of 10 to 60% by weight, preferably 20 to 50% by weight, and the content of the recording sensitivity enhancer is 5 to 40. Wt%, preferably in the range of 10 to 30 wt%.
    [624] In addition, by introducing an acidic developer into the thermal recording layer of the laser marking article of the present invention, the sensitivity can be improved and a vivid color tone can be provided to the laser marking article. As the acidic developer, the usual electron-accepting materials exemplified above are used.
    [625] In addition, in order to improve the sensitivity of the laser marking article of the present invention, a heat-fusible material can be introduced into the thermal recording layer. It is preferred that the thermoplastic material has a melting point of 60 ° C to 180 ° C, in particular 80 ° C to 140 ° C.
    [626] The color marking composition of the present invention can be obtained by using the colorless or light colored dye precursor, urea-urethane compound developer, recording sensitivity improver, aqueous binder, and water as essential components and mixing with various auxiliary agents as necessary. have.
    [627] The pH of the water used in the color marking composition is in the range of 5-12, preferably 6-9. If the pH is less than 5, fog is caused. If the pH is above 12, there may be undesirable effects such as loss of color development ability of the urea-urethane compound developer. In addition to water-soluble organic solvents such as methanol, ethanol and the like, water may be used.
    [628] In addition to the essential ingredients described above, various auxiliaries may also be incorporated into the color marking compositions used in the invention, if necessary, for example, in order to facilitate application of the composition on the support. Various adjuvants include, for example, dispersants (such as sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, lauryl alcohol sulfate ester sodium salts and fatty acid metal salts), opacifying agents (such as titanium oxide), antifoaming agents , Viscosity modifiers, fluorescent dyes and colorants.
    [629] The support on which the coloring marking composition of the present invention is printed (coated) is not particularly limited as long as it requires marking. As the support, mention is made of, for example, certain portions of food containers, packaging materials, electronic parts and the like, and articles attached thereto (eg, support for labels). As the support for the label, paper (for example, paper and synthetic paper), synthetic resin film, plastic, metal deposited paper and synthetic paper, metal deposited film, metal, wood and the like are suitably used depending on the application.
    [630] The color marking composition is prepared as follows, for example. The binder is dissolved or dispersed in water or a solvent based on water. Among a color developer, a developer, a recording sensitivity improver, etc., a ball mill is contained in water or an aqueous solvent containing a dispersant such as poly (vinyl alcohol) in water or a solvent containing water as a main component. One or more dispersions are prepared by treatment together or separately, using a disperser such as an attritor, sand grinder, and the like. The average particle size of each component after the dispersion operation is usually about 2 mu or less, preferably about 1 mu or less. Then, the binder and the dispersion are mixed to obtain the color marking composition of the present invention. The solids content of the color marking composition is 20 to 70% by weight, preferably about 30 to 65% by weight.
    [631] The color marking composition may be applied directly on the support, or may be applied on a support that has been previously surface treated, undercoated, or the like. For example, the application can be carried out using a suitable coater such as a roll coater, gravure coater, micro gravure coater, knife coater, spray coater and the like. The thickness (thermal recording layer) of the coating film obtained by application and drying can usually be adjusted to 1 to 4 mu. If the thickness is less than 1 mu, the color developer by laser irradiation is no longer sufficient, and the coating film tends to peel off. On the other hand, when thickness is over 4 micrometers, there exists a tendency for drying characteristic and label adhesion to fall. Drying is variable depending on the coating conditions such as the speed of the line, and can be performed at room temperature or by heating under conditions that do not cause color development of the thermal recording layer.
    [632] The protective layer of the laser marking article of the present invention is formed by applying a clear clear coating liquid to the thermal recording layer. The clear coating solution is an aqueous composition composed of an aqueous binder, water, and the like.
    [633] As the aqueous binder used in the clear coating liquid for the protective layer of the present invention, those obtained using a water-soluble or water-dispersible resin known per se, which is used in coating materials or inks, can be mentioned. Each of the above resins has a hydrophilic group (for example, a carboxyl group or an amino group) optionally introduced to impart water solubility or water dispersibility. As the resin for the aqueous binder, a resin having a glass transition temperature of 20 to 80 ° C, preferably 35 to 70 ° C is used. When the glass transition temperature is less than 20 ° C., the scratch resistance, chemical resistance, water resistance, and the like of the protective layer decrease. On the other hand, when glass transition temperature is more than 80 degreeC, a protective layer will be broken, a softness | flexibility etc. are bad, and it is easy to be cracked. Therefore, all of said glass transition temperatures are undesirable. If necessary, in addition to the components described above, a leveling agent, a slippering agent, an antifoaming agent, and the like may be introduced into the clear coating liquid.
    [634] As the aqueous binder used in the clear coating solution, the acrylic resin is mainly composed of alkyl (C1-C24) esters of acrylic acid or methacrylic acid, and includes, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid and maleic acid; Hydroxy-containing unsaturated monomers such as hydroxyethyl acrylate and hydroxypropyl methacrylate; Amino-containing unsaturated monomers such as acrylamide and methacrylamide; And other unsaturated monomers such as styrene, acrylonitrile, vinyl acetate, vinyl chloride, and the like, and can be obtained by copolymerizing the alkyl ester with the comonomer. The polyester resin can be obtained by ester reaction of a polybasic acid (including acid anhydride) having two or more carboxyl groups in a molecule with a polyhydric alcohol having two or more hydroxyl groups in a molecule. The glass transition temperature of the aqueous binder can be adjusted to any temperature by appropriately selecting the kind, combination and proportion of the components constituting the binder.
    [635] The clear coating solution is prepared by dissolving or dispersing the aqueous binder in suitable water, and if necessary, a leveling agent, a slippering agent, an antifoaming agent, and the like are introduced. The solids content of the clear coating solution is preferably in the range of 20 to 70% by weight, in particular 30 to 60% by weight.
    [636] The clear coating liquid may be printed (coated) on the surface of the dry coating film formed as the thermal recording layer. The printing (application) method is not particularly limited. Application can be performed using a roll coater, gravure coater, micro gravure coater, spray coater and the like.
    [637] The thickness of the formed coating film can usually be adjusted to 3 to 10 μ. If the thickness is less than 3 mu, the protection of the thermal recording layer calculated by the clear coating is insufficient, and the chemical resistance, the friction resistance, and the like decrease. On the other hand, when thickness is more than 10 micrometers, there exists a tendency for the drying characteristic and physical performance of the said coating film to fall. Drying of the clear coating liquid is variable depending on the coating conditions such as the speed of the line, and can be performed at room temperature or by heating under conditions that do not cause color development of the thermal recording layer.
    [638] When irradiating a laser beam to the heat-sensitive recording layer of the formed article for marking, the irradiated portion is heated so that the urea-urethane compound developer and the dye precursor react with each other, thereby coloring and marking. The amount of energy of the laser beam used for the irradiation is not particularly limited, but considering the possibility of breaking the coating film, it is preferable that it is 1.4 J (joule) / cm 2 or less. On the other hand, the lower limit of the amount of energy required for color development is unclear because there is no device capable of generating low energy, but sufficient color development occurs even at an energy amount of 0.4 J / cm 2 . Thus, the amount of energy suitable for color development by irradiation is in the range of 0.4 to 1.4 J / cm 2 , in particular 0.45 to 1.2 J / cm 2 . As the laser used for the irradiation, a pulse laser or a scanning laser is suitable. Regarding the type of laser, for example, any gas laser, excimer laser and semiconductor laser can be used. Specific examples of the laser are carbon dioxide laser, mixed gas laser, YAG laser, ruby laser and the like.
    [639] CLAIMS What is claimed is: 1. A method of irradiating a laser beam onto a portion of a desired shape, comprising: irradiating a coating beam with a laser beam on a coating film to correspond to a shape of an opening of the metal mask; And a method of irradiating a laser onto the coating film according to the desired form by inputting the desired form by a computer and using a single stroke using a single stroke. When irradiating a laser beam to the thermal recording layer, the temperature of the irradiated portion is increased, causing color development by melting and mixing of the thermal recording layer, so that letters or drawings of a definite purpose form appear. The color change by irradiation can be performed instantaneously because the energy density of the laser beam is high.
    [640] The label as an article for laser marking of the present invention is formed on a support for a label appropriately selected according to the purpose from paper (e.g., paper and synthetic paper), synthetic resin film, plastic, metal deposited paper and synthetic paper, metal deposited film, metal, and the like. Can be produced by forming the thermal recording layer and the protective layer by the above-mentioned method. The labels obtained can be used in all fields of conventional labels, but are preferably used in the fields of food, pharmaceuticals, toiletry, publications, and electrical and electronic components, in particular.
    [641] The packaging material as the article for laser marking of the present invention is suitably in accordance with the purpose in paper (for example, paper and synthetic paper), synthetic resin film, plastic, metal-deposited paper and synthetic paper, metal-deposited film, metal, glass, wood, etc. On any of various conventional packaging materials such as boxes, wrapping papers and packages obtained using the selected support, it is produced by forming the thermal recording layer and the protective layer by the above-mentioned method. The packaging material obtained can be used in all fields of conventional packaging materials, but is particularly preferably used in the fields of food, medicine, toys, publications, and electrical and electronic components.
    [642] The container as the article for laser marking of the present invention is produced by forming a thermal recording layer and a protective layer on the support such as glass, plastic, metal or the like by the above-mentioned method. The food containers can be used in all fields of conventional food containers, such as bottles of liquor and soft drinks, retort food containers, instant food containers, cosmetic containers, pharmaceutical containers, toetree products and the like.
    [643] When the color developing composition of the present invention is used in a pressure-sensitive recording material, the recording material may have a form disclosed in, for example, US Patent Application Nos. 2505470, 2712507, 2730456, 2730457, 3418250, and the like. . That is, various forms, such as the following forms, can be used: alone or two of alkylated naphthalene, alkylated diphenyl, alkylated diphenylmethane, alkylated diarylethanes, synthetic oils (eg, chlorinated paraffins), vegetable oils, animal oils, mineral oils, and the like. In a solvent composed of the above mixture, a dye precursor or a mixture of dye precursors is dissolved and the resulting solution is dispersed in a binder, the solution is introduced into a microcapsule, the dispersion is applied onto a support, or the microcapsules are binders. Obtained by applying on the support together with the upper layer paper and the lower layer paper coated with the dispersion of the urea-urethane compound (and amino compound and / or developer, etc.) obtained as described above so that the coated surfaces face each other. Decompressed recording paper; Between the upper and lower layers mentioned above, a pressure-sensitive recording paper obtained by sandwiching an intermediate sheet coated with a dispersant of a urea-urethane compound and one surface coated with a dye precursor; Self-type pressure-sensitive recording paper obtained by applying the dispersion of the urea-urethane compound (and amino compound and / or developer) and the dye precursor-containing dispersion as a mixture on the same surface of the support or in a multilayered form. ; And magnetic pressure recording paper obtained by microencapsulating each of the dye precursor and the urea-urethane compound (and amino compound and / or developer) and applying a mixture of two microcapsules on the same surface of the support.
    [644] As a preparation method of the microcapsules, for example, the coacervation method disclosed in US Patent Application Nos. 2800457 and 2800458, JP-B-38-19574, JP-B-42-446, JP-B The interfacial polymerization method disclosed in -42-771, etc., the in-situ method disclosed in JP-B-36-9168, JP-B-51-9079, etc., melt dispersion disclosed in British Patent Nos. 952807 and 965074, and the like. Cooling methods and the spray drying methods disclosed in US Pat. No. 311140, UK Pat. No. 930422, and the like may be employed.
    [645] The color development composition of this invention corresponds to the compound of the dye precursor and the developer as described in each said reference example.
    [646] To form the pressure-sensitive recording layer, each component, such as a urea-urethane compound, may be used in the form of a solution or a dispersion in a solvent. In addition, in the case of a color development system containing an amino compound and / or a developer, each component may be used in the form of a dispersion in a solution or a solvent, or a urea-urethane compound, an amino compound is used, and optionally a developer is used. It can be used in the form of a dispersion in solution or in a solvent.
    [647] In the above-described interfacial polymerization method employed to form microcapsules, a film is formed on the interface using two kinds of monomers, namely, an oily monomer and a water-soluble monomer. For example, a method of using polybasic acid chloride as the oily phase and using polyhydric amine as the aqueous phase and forming a polyamide film on the interface; A method of using a polybasic acid chloride as an oily phase and using a polyvalent hydroxy compound as an aqueous phase to form a polyester film on the interface; A method of using a polyisocyanate as an oil phase and using a polyhydric alcohol or a polyhydric phenol as the aqueous phase and forming a polyurethane film on the interface; And a method of forming a polyurea film on an interface using polyhydric isocyanate as the oily phase and polyhydric amine as the aqueous phase. Thus, when the interfacial polymerization process is adopted for the production of microcapsules, isocyanate compounds are used in some cases as reactive monomers for film formation.
    [648] In this case, the isocyanate compound is consumed to form the film for microcapsules and is not directly related to the color burned image, and it is entirely necessary to use a water soluble monomer together with the isocyanate compound. In this respect, its use is distinguished from the use of isocyanate compounds according to the invention.
    [649] Dispersions of unmicroencapsulated compounds are prepared by finely grinding one or more compounds as each component in an aqueous solution containing a compound having a dispersing ability such as a water-soluble polymer or a surfactant. The urea-urethane compound may be dispersed together with an amino compound and an acidic developer.
    [650] As the support used for the thermal recording material, paper is mainly used, but besides the paper, any of various woven fabrics, nonwoven fabrics, synthetic resin films, laminated papers, synthetic papers, metal foils, and composite sheets obtained by combining two or more of the above Can be used depending on the purpose.
    [651] As the binder, various conventional binders can be used. The binder is, for example, starch, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, poly (vinyl alcohol), modified poly (vinyl alcohol), sodium poly (acrylate), acrylamide-acrylic acid ester Water-soluble binders such as copolymers, acrylamide-acrylic acid ester-methacrylic acid terpolymers, alkali salts of styrene-maleic anhydride copolymers, alkali salts of ethylene-maleic anhydride copolymers, and the like; And latex-based water-insoluble binders such as styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and methyl acrylate-butadiene copolymer.
    [652] In the recording material of the present invention, the recording layer may contain a hindered phenol compound or an ultraviolet absorber. The hindered phenolic compound or ultraviolet absorber is, for example, 1,1,3-tris (3'-cyclohexyl-4'-hydroxyphenyl) butane, 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3 , 5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, p-octylphenyl salicylate, 2- (2'- Hydroxy-5'-methylphenyl) benzotriazole, ethyl-2-cyano-3,3'-diphenyl acrylate and tetra (2,2,6,6-tetramethyl-4-piperidyl) -1 , 2,3,4-butanetetracarbonate.
    [653] The method for forming the coloring layer is not particularly limited. The chromophoric layer is, for example, free-fall curtain coating, air-knife coating, Barriber blade coating, Pure blade coating, short-dwell The coating liquid for a coloring layer is apply | coated on a support body by suitable coating methods, such as coating), and it is formed by drying the processed support body. Although the coating amount of the coating liquid for a coloring layer is not restrict | limited, It is adjusted to the range of 1-15 g / m <2> , Preferably it is about 3 to about 10 g / m <2> by dry weight.
    [654] Thermal response can be improved by forming an intermediate layer between the thermal recording layer and the support. In the case of the conventional thermal recording material, a technique for improving color sensitivity, for example, by jointly using a heat-fusible material in a color developing layer has been used. The improvement of the sensitivity by the above method is disadvantageous in that fog is likely to be caused by heat or friction. This facilitates the generation of fog, especially in the thermal recording material obtained using the urea-urethane compound developer having excellent color sensitivity. In the case of a conventional thermal recording material without print preservation, even when fog is generated, it disappears like printing, and therefore fog is hardly considered, especially when using a recording material after long time storage. However, in the case of the thermal recording material obtained by using the urea-urethane compound developer, which is particularly excellent in long-term printing preservation, in some cases, the following problem is caused: once fog is generated, it is preserved, so Is stored and accumulated each time it is used, the surface of the recording material becomes dirty when the recording material is used after long time storage. In this case, by forming the intermediate layer, substantial color sensitivity can be achieved by not using a heat-fusible material or by using only a small amount of the heat-fusible material, and resisting fog caused by heat or friction. This is so excellent that even when the recording material is used after long time storage, a thermal recording material can be obtained in which little fog is accumulated.
    [655] The interlayer consists mainly of organic or inorganic pigments, hollow particles, and aqueous binders such as water soluble polymers or latexes. As the organic or inorganic pigments and the aqueous binder, the same organic or inorganic pigments and aqueous binders as used in the above-mentioned thermal recording layer can be used. The method for forming the intermediate layer is not particularly limited. As the above method, the same method as that for forming the thermal recording layer can be employed. The dry coating amount for forming the intermediate layer is preferably in the range of 2.0 to 15.0 g / m 2 . In this case, the surface pH of the intermediate layer formed on the support is preferably 3 to 9, more preferably 5 to 9 and most preferably 6 to 8.
    [656] Further, in the present invention, the friction resistance of the obtained recording paper can be improved by forming a protective layer mainly composed of a water-soluble polymer on the thermal recording layer, if necessary. When the urea-urethane compound developer of the present invention excellent in color development sensitivity and printing resistance to long-term storage is used, the traces of friction tend to remain because the sensitivity is high. On the other hand, once the remaining traces of friction are preserved for an indefinite time, every time the recording material is stored and used, the traces of friction accumulate. Therefore, in some cases, when the recording material is used after long time storage, the surface of the paper becomes dirty. In some cases, by forming the protective layer, even if the recording paper is used after long time storage, it may be difficult to produce a rubbing trace. Specific examples of the water-soluble polymer contained in the protective layer are the water-soluble polymer binders mentioned in connection with the thermal recording layer. The water soluble polymer can be used with conventional waterproofing agents that can waterproof the water soluble polymer. Specific examples of the waterproofing agent are formaldehyde, glyoxal, chromium alum, melamine, melamine-formaldehyde resin, polyamide resin, polyamide-epichlorohydrin resin and the like.
    [657] In addition, pigments, metal soaps, waxes, crosslinking agents and the like are introduced into the protective layer for the purpose of, for example, improving the matching with the thermal head during printing and improving the water resistance of the protective layer. .
    [658] Pigments include zinc oxide, calcium carbonate, barium sulphate, titanium oxide, lithopone, talc, pagodite, kaolin, aluminum hydroxide, silica, amorphous silica and the like. The amount of the pigment to be added is 0.5 to 4 times, preferably 0.8 to 3.5 times the total weight of the polymer. If the amount is below the lower limit of the range, the pigment is not effective to improve the matching with the thermal head. When the above amount exceeds the upper limit, the sensitivity of the thermal recording material is significantly lowered, so that the commercial value of the recording material is lowered.
    [659] Metal soaps are, for example, emulsions of higher fatty acid metal salts such as zinc stearate, calcium stearate, aluminum stearate and the like. The metal soap is added in a proportion of 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the protective layer. Waxes include, for example, emulsions of paraffin wax, microcrystalline wax, carnauba wax, methylolstearoamide, polyethylene wax and the like. The wax is added in a proportion of 1 to 20% by weight, preferably 1 to 10% by weight, based on the total weight of the protective layer.
    [660] In forming the protective layer on the thermal recording layer, a surfactant is added to the coating liquid for forming the protective layer in order to form a uniform coating layer. The said surfactant contains alkali metal salts, such as sulfosuccinic acid and a fluorine-containing surfactant. Specific examples of the surfactant are sodium salts or ammonium salts such as di- (2-ethylhexyl) sulfosuccinic acid and di- (n-hexyl) sulfosuccinic acid. In general, any surfactant is effective as long as it is anionic. In addition, conventional auxiliary additives such as fillers, heat-fusible materials (lubricants), surfactants, fluorescent pigments and the like may be introduced into the protective layer. Specific examples of the filler, the heat-fusible material, and the fluorescent pigment are those mentioned in connection with the thermal recording layer. The dry coating amount of the protective layer is preferably about 0.5 to about 10 g / m 2 , in particular about 1 to about 5 g / m 2 .
    [661] If necessary, when a reverse-side layer (back coating layer) is formed on the opposite side of the recording layer of the recording material produced by the method of the present invention, it may be difficult to produce curl of the obtained recording paper. In particular, in the case of the urea-urethane compound developer of the present invention, the formation of the backing layer is effective for the following reasons: The developer has better dispersibility than other developer and easily obtains a dispersion having a small particle size. When the coating solution prepared by mixing the developer and other necessary ingredients is coated on the support, the cohesive force of the binder increases during drying due to the small particle size of the binder, so that the recording layer is easily contracted and curls are generated. easy. As the components of the coating liquid for the back layer and the coating method for the coating liquid, the same components and methods as in the case of the protective recording layer can be used. The dry coating amount of the coating liquid is preferably in the range of 0.2 to 10.0 g / m 2 .
    [662] The invention is explained in more detail using the following examples.
    [663] Material analysis and physical property evaluation were performed by the following method.
    [664] [IR spectrum]
    [665] Shimadzu Corp. It is measured by diffuse reflection spectroscopy using FTIR-8100M manufactured by.
    [666] [Mass spectrum]
    [667] JEOL LTD. Using JMS-HX100 manufactured, nitrobenzyl alcohol is measured as matrix and xenon as primary gas.
    [668] [Color Sensitivity of Thermal Paper]
    [669] Ohkura Denki K.K. Manufacturing testing machine, and Kyocera Co., Ltd. Using the thermosensitive head KJT-256-8MG, the color development density in a voltage of 24 V and a pulse width of 1.5 msec was measured with an optical density meter.
    [670] [Plasticizer resistance]
    [671] The thermal recording material was inserted between vinyl chloride wrap films or in vinyl chloride piles and a load of 300 g / cm 2 was applied from above. After standing at 40 ° C. for 24 hours, the color density of the print portion and the non-print portion (original recording material surface) were visually evaluated. When the print density is only slightly reduced, print preservation is evaluated to be good.
    [672] [Heat resistance]
    [673] The thermal recording material was left at 60 ° C. at 25% RH for 24 hours, and the degree of fading of printing was visually evaluated. If the degree of fading is low, the printability is evaluated to be good.
    [674] In addition, the thermal recording material was left at 80 ° C. and 25% RH for 24 hours, and the degree of fading of printing was visually evaluated. If the degree of fading is low, the printability is evaluated to be good. In addition, the color development density of the original recording material surface was visually evaluated. When the color development is weak, the preservation of the surface of the print recording material is evaluated to be good.
    [675] [Color density of pressure sensitive paper]
    [676] The upper and lower layers are superimposed so that the coated surfaces face each other. Pressure was applied to it from above to obtain an image developed on the lower layer. The color density of the color image was measured using a densitometer Macbeth RD917.
    [677] [Solvent resistance]
    [678] In the color development concentration evaluation, a hand cream (Atrix, trade name, manufactured by Kao Corp.) was applied thinly to the obtained color development image portion, and left at room temperature for 7 days, and then the color development concentration of the printed portion was visually evaluated. If print density is only slightly reduced, print preservation is evaluated to be good.
    [679] Example 1
    [680] To 27.8 g of 2,4-toluene diisocyanate, 111 g of toluene was added as a solvent, and then a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature over 1 hour, and the reaction was further performed for 1 hour. . The precipitated white solid was collected by filtration, washed with hexane and dried in vacuo overnight to yield 20 g of white crystals. Subsequently, 5 g of the obtained compound was added to 50 mL of methanol, and the reaction was performed at 60 ° C. for 30 minutes, and then excess methanol was removed using an evaporator, and the residue was crystallized by addition of toluene. The obtained white crystals were collected by filtration, washed with hexane and dried in vacuo overnight to yield 5.4 g of white crystals. The melting point of the white crystals was 196 ° C.
    [681] The analytical value of the white crystal is as follows.
    [682] Result of IR measurement:
    [683] The characteristic peaks were found at 1060 cm -1 , 1250 cm -1 , 1600 cm -1 , 1650 cm -1 , 1670 cm -1 , 1700 cm -1 and 3300 cm -1 .
    [684] The chemical formula of the main component of the compound is estimated by the chemical formula of the compound (S-1).
    [685] Then, 2 g of the compound was pulverized and dispersed in a paint shaker for 6 hours with 8 g of an aqueous solution of 2.5 wt% poly (vinyl alcohol) (Gohseran L-3266, trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and then dispersed. Prepared. The temperature of the dispersion liquid immediately after the dispersion operation was 25 ° C. The diameter of the dispersed particles of the compound was about 0.6 μm.
    [686] 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane together with 130 g of an 8% by weight poly (vinyl alcohol) aqueous solution was added at 2000 rpm in a sand grinder (manufactured by AIMEX CO., LTD .; pipe volume 400 mL). Another dispersion was prepared by grinding and dispersing for 3 hours at rotational speed.
    [687] Further, 70 g of diphenylsulfone was ground and dispersed in a sand grinder (manufactured by AIMEX CO., LTD .; pipe volume: 400 mL) with 130 g of a 5.4 wt% poly (vinyl alcohol) aqueous solution for 3 hours at a rotational speed of 2000 rpm. A dispersion was prepared.
    [688] In addition, 10 g of calcium carbonate and 30 g of water were mixed, and another dispersion was obtained by stirring the mixture using a stirrer.
    [689] The dispersion and the other components were stirred and mixed in the following proportions (dry reference ratio) to obtain a coating solution: 30 parts by weight of a dry solid of the dispersion of the compound, 3-dibutylamino-6-methyl-7 15 parts by weight of the dry solids of the anilinofluorane dispersion, 30 parts by weight of the dry solids of the diphenyl sulfone dispersion, 20 parts by weight of the dry solids of the calcium carbonate dispersion, and dry solids of the zinc stearate dispersion (solid content of 16% by weight). 10 parts by weight, and 7 parts by weight of dry solids of 15% by weight of poly (vinyl alcohol).
    [690] The coating solution was applied onto a base paper having a reference weight of 50 g / m 2 using the bar coater of No. 10. After drying, supercalendering was performed to obtain a thermal recording material. The coating amount of the coating liquid was 4 g / m 2 in dry weight.
    [691] The sensitivity evaluation result of the obtained thermal recording material was favorable with optical density 1.2. Originally, evaluation results of the degree of color change (heat resistance) due to heat on the surface of the recording material were small in color change and were good. The fading by heat of the printing part was also small and preferable. The evaluation results are summarized in Table 1.
    [692] Example 2
    [693] After adding 40 g of methyl ethyl ketone as a solvent to 17 g of 2,4-toluene diisocyanate, 3.8 g of methanol was added dropwise thereto, and the reaction was carried out at 60 ° C. for 5 hours with stirring. Subsequently, 9.9 g of 4,4'-diaminodiphenyl sulfone was added thereto, and the reaction was performed with stirring at 60 ° C for 4 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, 800 g of acetonitrile was poured, the precipitated crystals were collected by filtration, washed with hexane, and then dried in vacuo overnight to yield 15 g of compound as white crystals.
    [694] The melting point of the white crystal was 169 ° C., and its analysis value is as follows.
    [695] Result of IR measurement:
    [696] The characteristic peaks were found at 1220 cm −1 , 1550 cm −1 , 1590 cm −1 , 1660 cm −1 , 1740 cm −1, and 3300 cm −1 .
    [697] Results of mass spectral measurements:
    [698] [M + H] + was detected at m / z 661.
    [699] The chemical formula of the main component of the compound is estimated by the chemical formula of the compound (S-13).
    [700] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the obtained compound instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [701] Example 3
    [702] 3.46 g of aniline was dissolved in 100 mL of ethyl acetate, and the obtained solution was stirred at room temperature. A solution of 10 g of trimethylolpropane adduct (Coronate L, trade name, manufactured by Nippon Polyurethane Industry Co. Ltd .; 75% ethyl acetate solution) of toluene diisocyanate was added dropwise thereto in 50 mL of ethyl acetate. The reaction was further performed for 30 minutes. The crystals formed were collected by filtration and dried in vacuo overnight to give 5.1 g of the compound as white crystals. The melting point of the white crystal was 161 ° C, its analysis value is as follows.
    [703] Result of IR measurement:
    [704] The characteristic peaks were found at 1070 cm -1 , 1220 cm -1 , 1550 cm -1 , 1600 cm -1 , 1700 cm -1, and 3300 cm -1 .
    [705] The chemical formula of the main component of the compound is estimated by the chemical formula of the compound (S-33).
    [706] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the obtained compound instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [707] Example 4
    [708] To 10.4 g of 2,4-toluene diisocyanate, 20 g of methyl ethyl ketone is added as a solvent, and then a dilution of 3.7 g of 4,4'-diaminodiphenyl sulfone using 30 g of methyl ethyl ketone is added dropwise thereto, and the reaction is carried out. Was carried out at room temperature for 20 hours. After completion of the reaction, methyl ethyl ketone was concentrated and removed, toluene was added to the residue, the precipitated white solid was collected by filtration, washed with hexane, and then dried in vacuo overnight to yield 8.8 g of compound as white crystals. did. Subsequently, 15 g of phenol, and then a small amount of dibutyltin dilaurate were added to 4 g of the obtained compound, and the reaction was carried out at 50 ° C. for 4 hours. After completion of the reaction, toluene was added to the reaction solution, and the precipitated crystals were collected by filtration, washed with hexane, and then vacuum dried overnight to obtain 5.2 g of a urea-urethane compound as white crystals.
    [709] To 10 g of 2,4-toluene diisocyanate, 30 g of toluene was added as a solvent, and then 30 g of phenol was added thereto, and the reaction was carried out at 100 ° C. for 3 hours. After completion of the reaction, toluene was concentrated and removed, and hexane was added to the residue. The precipitated white crystals were collected by filtration, washed with hexane, and then vacuum dried overnight to obtain 15 g of a urethane compound as white crystals.
    [710] The chemical formula of the main component of the compound is estimated by the chemical formula of the following compound (C-2).
    [711] Subsequently, 3 g of the urea-urethane compound and 2 g of the urethane compound were mixed to obtain a urea-urethane composition. Thereafter, 2 g of the urea-urethane composition was pulverized and dispersed in a paint shaker for 45 minutes together with 8 g of 2.5 wt% aqueous methyl cellulose solution to obtain a dispersion.
    [712] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except that instead of using the dispersion of the compound obtained in Example 1, the dispersion of the composition was used. The results obtained are summarized in Table 1.
    [713] Example 5
    [714] Instead of using the urea-urethane composition used in Example 4, except that 4.5a of the urea-urethane compound synthesized in Example 4 and 0.5g of the urethane compound were used, except that the urea-urethane composition was used. In the same manner, the thermal recording material was produced and evaluated. The results obtained are summarized in Table 1.
    [715] Example 6
    [716] Instead of the urea-urethane composition used in Example 4, after synthesis reaction of the urea-urethane compound and before precipitation by addition of toluene, 2.2 g of diphenyl sulfone is added to the reaction system, and the obtained mixture is stirred, and The urea-urethane composition obtained in the same manner as in Example 4, except that toluene was added to the mixture to recover the precipitated crystals, the crystals were washed with hexane, and the crystals were vacuum dried overnight. The thermal recording material was produced and evaluated in the same manner as in Example 4 except that g was used. The results obtained are summarized in Table 1.
    [717] Example 7
    [718] To 31.5 g of 2,4-toluene diisocyanate, a solution of 21.5 g of 4,4'-diaminodiphenyl sulfone in MEK 60 mL was added dropwise while stirring at 70 to 300 to 500 rpm over 4 hours, and the reaction was carried out. A further run for 4 hours gave a white viscous slurry reaction mixture. The reaction mixture was then cooled to 50 ° C., 17.1 g of phenol was poured into the reaction mixture and dissolved therein, and thereafter 0.015 g of triethylamine was added as a catalyst, and the reaction was carried out for 4 hours to give a yellow transparent A viscous reaction mixture was obtained. The reaction mixture was desolvated and concentrated to solidify under reduced pressure, and the obtained solid was triturated and then dried in vacuo overnight to yield about 70 g of a urea-urethane composition as a pale yellow powder.
    [719] The melting point of the pale yellow powder was 160 to 180 ° C. In the IR measurements of the powder, the broad peak formed by the superposition of the characteristic peaks attributed to each of the urea and urethane groups appeared at about 1700 cm −1 .
    [720] The content of the urea-urethane main component in the urea-urethane composition was 68% as measured by liquid chromatography.
    [721] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the above-mentioned composition instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [722] Example 8
    [723] To 158.5 g of 2,4-toluene diisocyanate, 240 g of methyl ethyl ketone is added as a solvent, and 107.5 g of 4,4'-diaminodiphenyl sulfone is powdered therein over 30 hours at 400 ° C. at 400 rpm. It was added with stirring. After 1 hour, 26 g of methyl ethyl ketone was added thereto, and further stirred for 15 minutes to obtain a white viscous slurry reaction mixture. Then, a solution of 89.5 g of phenol in 15.8 g of methyl ethyl ketone was poured into the reaction mixture to dissolve, and then 9.3 g of a 1% by weight solution of triethylamine in methyl ethyl ketone was added as a catalyst over 2 hours, and the reaction was carried out in 1 Continued for hours. Thereafter, the reaction mixture was cooled to 20 ° C. and stirred for 3 hours to obtain a slurry containing pale yellow crystals deposited thereon. The slurry was desolvated under reduced pressure, concentrated to solidify, the solid obtained was triturated and then vacuum dried overnight to yield 355 g of urea-urethane composition as a pale yellow powder.
    [724] The melting point of the pale yellow powder was 130 to 170 ° C. In the IR measurements of the powder, the broad peak formed by the superposition of the characteristic peaks attributed to each of the urea and urethane groups appeared at about 1700 cm −1 . The content of urea-urethane main component in the urea-urethane composition was 65% as measured by liquid chromatography.
    [725] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the above-mentioned composition instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [726] Example 9
    [727] To 27.8 g of 2,4-toluene diisocyanate, 100 g of toluene was added as a solvent, and a solution of 7.4 g of aniline in 37 g of toluene was added dropwise at room temperature over 1 hour, and the reaction was further performed for 1 hour. The precipitated white solid was collected by filtration, washed with hexane and dried in vacuo overnight to yield 20 g of white crystals. Subsequently, 5 g of the obtained compound was added to 50 mL of methanol, and the reaction was carried out at 60 ° C. for 30 minutes, then excess methanol was removed using an evaporator, and the residue was vacuum dried overnight to give urea-urethane composition 5.4 g was obtained as white crystals. The melting point of the white crystals was 196 ° C. Upon IR measurement of the crystals, the characteristic peaks due to the urea-urethane compound were found at 1670 cm −1 and 1700 cm −1 . The content of the urea-urethane main component in the urea-urethane composition was 92% as measured by liquid chromatography.
    [728] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the above-mentioned composition instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [729] Example 10
    [730] To 17 g of 2,4-toluene diisocyanate, 40 g of methyl ethyl ketone was added as a solvent, 3.8 g of methanol was added dropwise thereto, and the reaction was carried out at 60 ° C. for 5 hours with stirring. Subsequently, 9.9 g of 4,4'-diaminodiphenyl sulfone was added thereto, and the reaction was carried out with stirring at 60 ° C for 4 hours. After completion of the reaction, methyl ethyl ketone as solvent was removed using an evaporator and the residue was dried in vacuo overnight to give 16 g of urea-urethane composition as white crystals. The melting point of the white crystals was 169 ° C. In the IR analysis of the crystals, the characteristic peaks due to the urea-urethane compound were found at 1660 cm −1 and 1740 cm −1 . The content of urea-urethane main component in the urea-urethane composition was 52% as measured by liquid chromatography.
    [731] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the above-mentioned composition instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [732] Example 11
    [733] 27.5 g of 2,4-toluene diisocyanate was dissolved in 253 mL of toluene, and a solution of 14.7 g of aniline in 85 mL of toluene was added dropwise with stirring over 30 minutes at 40 ° C. at 200 rpm, and the reaction was carried out for 30 minutes. While more performed. To the white slurry obtained, 18.0 g of 2,2-bis (4-hydroxyphenyl) propane, 262 mL of toluene and 0.42 mg of triethylamine as a catalyst were added, and the stirring speed was increased to 400 rpm. In order to prevent agglomeration of particles in the slurry in the initial reaction by controlling the reaction rate, the reaction is carried out by raising the reaction temperature stepwise as follows: 5 hours at 60 ° C., 2 hours at 65 ° C., 1 at 70 ° C. Hour and 1 hour at 75 ° C. Then 0.42 mg of triethylamine was added and the reaction was further performed at 80 ° C. for 8 hours. The reaction mixture was cooled to room temperature and the white crystals obtained were collected by filtration. The white crystals were dried in vacuo overnight to give 59 g of urea-urethane composition as white crystals. Melting | fusing point of the said white crystal was 170 degreeC. In the IR analysis of the crystal, a broad characteristic peak attributable to the urea-urethane compound was found at 1720 cm −1 . The content of urea-urethane main component in the urea-urethane composition was 81% as measured by liquid chromatography.
    [734] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the above-mentioned composition instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [735] Examples 12-23
    [736] Instead of diphenylsulfone, 4,4'-dichlorodiphenyl sulfone (Example 12), 4,4'-dihydroxydiphenyl sulfone (Example 13), 2,4'-dihydroxydiphenyl sulfone ( Example 14), 4- (benzyloxy) phenol (Example 15), salicyanylide (Example 16), 4,4'-diaminodiphenyl sulfone (Example 17), 4,4'-dichlorobenzo Phenone (Example 18), 4,4'-diaminodiphenylmethane (Example 19), 4,4'-dimethoxybenzophenone (Example 20), diphenyl carbonate (Example 21), 4 A thermal recording material was prepared in the same manner as in Example 8, except that 4'-dimethoxydiphenyl sulfone (Example 22) or 4,4'-diallyloxydiphenyl sulfone (Example 23) was used. It produced and evaluated the said thermal recording material. The results obtained are summarized in Table 1.
    [737] Comparative Example 1
    [738] A thermal recording material was produced and evaluated in the same manner as in Example 1, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [739] Comparative Example 2
    [740] To 17.4 g of 2,4-toluene diisocyanate, 5 mL of methyl ethyl ketone was added as a solvent, and a solution of 3.2 g of methanol in 5 mL of methyl ethyl ketone was added dropwise, and the reaction was performed with stirring at room temperature for 2 hours. Then, a solution of 7.3 g of n-butylamine in 100 mL of methyl ethyl ketone was added dropwise while stirring at room temperature, and the obtained mixture was stirred for 1 hour. The precipitated crystals were collected by filtration, washed with hexane and dried in vacuo overnight to give 27 g of compound as white crystals. The melting point of the white crystal was 156 ℃, its analysis value is as follows.
    [741] Result of IR measurement:
    [742] The characteristic peaks were found at 1240 cm −1 , 1550 cm −1 , 1640 cm −1 , 1720 cm −1, and 3300 cm −1 .
    [743] The estimated chemical formula of the main component of the compound is the following formula R-1.
    [744] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 1 except for using the obtained compound instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [745] Comparative Example 3
    [746] 100 g of toluene was added to 10.0 g of 2, 4-toluene diisocyanate. While stirring the obtained mixture at 25 ° C, a solution of 15.5 g of stearylamine in 100 mL of toluene was added thereto, and the reaction was continued at 25 ° C for 22 hours. After the completion of the reaction, the precipitated white solid was collected by filtration, washed with toluene, and then dried in vacuo overnight to give 20.4 g of white crystals. Thereafter, 5 g of the obtained compound was added to 50 mL of methyl ethyl ketone. While stirring the resulting mixture at 80 ° C., a solution of 8.6 g of p-hydroxybenzylcarboxylic acid in 20 mL of methyl ethyl ketone, and then 5 mg of dibutyltin laurate as a catalyst are added thereto, and the reaction is carried out at 80 ° C. Continued for 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with methyl ethyl ketone, and then vacuum dried overnight to obtain 5.6 g of white crystals.
    [747] The analytical value of the white crystal is as follows.
    [748] Result of IR measurement:
    [749] The characteristic peaks were found at 1220 cm -1 , 1520 cm -1 , 1630 cm -1 , 1710 cm -1 , 2900 cm -1 and 3300 cm -1 .
    [750] Mass spectral measurement results:
    [751] [M + H] + was detected at m / z 596.
    [752] The putative formula of the main component of the compound is the formula R-2 below.
    [753] A thermal recording material was produced and evaluated in the same manner as in Example 1, except that the obtained compound was used instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [754] Comparative Example 4
    [755] 3.0 g of p-aminophenol was added to 100 mL of dioxane. While stirring the obtained mixture at 50 ° C, a solution of 5.4 g of toluene sulfonyl isocyanate in 30 mL of dioxane was added dropwise over 1 hour, and the reaction was continued at 50 ° C for 5 hours. After the completion of the reaction, the reaction solution was concentrated, then poured into hexane to crystallize, and the precipitated solid was collected by filtration, washed with hexane and dried in vacuo overnight to give 4.9 g of brown crystals. Thereafter, 2 g of the obtained compound was added to 50 mL of dioxane. While the obtained mixture was stirred at 80 ° C., a solution of 3.8 g of octadecyl isocyanate in 10 mL of dioxane, and then 2 mg of dibutyltin laurate as a catalyst was added thereto, and the reaction was continued at 80 ° C. for 20 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with dioxane and then vacuum dried overnight to obtain 2.7 g of pale pink crystals.
    [756] The analyzed value of the light pink crystal is as follows.
    [757] Result of IR measurement:
    [758] The characteristic peaks were found at 1230 cm -1 , 1470 cm -1 , 1510 cm -1 , 1570 cm -1 , 1620 cm -1 , 1700 cm -1 , 2900 cm -1 and 3300 cm -1 .
    [759] The putative formula of the main component of the compound is the formula R-3 below.
    [760] A thermal recording material was produced and evaluated in the same manner as in Example 1, except that the obtained compound was used instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [761]
    [762] Comparative Example 5
    [763] To 10 g of 2,4-toluene diisocyanate, 50 g of toluene was added as a solvent, and 30 g of aniline was added thereto, and then the reaction was carried out at 25 ° C. for 3 hours. After the completion of the reaction, the precipitated white crystals were collected by filtration, washed with hexane, and then vacuum dried overnight to obtain 17 g of a compound as white crystals.
    [764] The estimated chemical formula of the main component of the compound is a chemical formula of the following compound (C-1).
    [765] Thereafter, 2 g of the compound was pulverized and dispersed in a paint shaker for 45 minutes with 8 g of 2.5 wt% aqueous poly (vinyl alcohol) solution to obtain a dispersion.
    [766] Subsequently, the thermal recording material was produced and evaluated in the same manner as in Example 1 except that the dispersion of the compound was used instead of the dispersion of the compound obtained in Example 1. The results obtained are summarized in Table 1.
    [767] Comparative Example 6
    [768] To 10 g of 2,4-toluene diisocyanate, 30 g of toluene was added as a solvent, and 30 g of phenol was added thereto, and then the reaction was carried out at 100 ° C. for 3 hours. After the completion of the reaction, toluene was concentrated and removed, hexane was added to the residue, and the precipitated white solid was collected by filtration, washed with hexane, and then dried in vacuo overnight to give 15 g of a compound as white crystals.
    [769] The estimated chemical formula of the main component of the compound is a chemical formula of the following compound (C-2).
    [770] Thereafter, 2 g of the obtained compound was pulverized and dispersed in a paint shaker for 45 minutes with 8 g of 2.5 wt% aqueous poly (vinyl alcohol) solution to obtain a dispersion.
    [771] Subsequently, the thermal recording material was produced and evaluated in the same manner as in Example 1 except that the dispersion of the compound was used instead of the dispersion of the compound obtained in Example 1. The results obtained are summarized in Table 1.
    [772]
    [773] Comparative Example 7
    [774] A thermal recording material was produced and evaluated in the same manner as in Example 1, except that 1,3-diphenylurea was used instead of the urea-urethane compound synthesized in Example 1. The results obtained are summarized in Table 1.
    [775]
    [776] 1. The sensitivity increases with increasing optical density (OD value).
    [777] 2. Plasticizer resistance (print preservation)
    [778] ◎-It does not fade substantially.
    [779] There is slight change in hue, but there is no scratch.
    [780] Discoloration markedly.
    [781] X ~ The color tone of printing disappears completely.
    [782] 3. Heat resistance (printing storage at 60 ℃)
    [783] ◎-It does not fade substantially.
    [784] There is slight change in hue, but there is no scratch.
    [785] Discoloration markedly.
    [786] X ~ The color tone of printing disappears completely.
    [787] 4. Heat resistance (preservation of the original recording material surface at 80 ° C)
    [788] -Practically no fog is caused.
    [789] Although there is a slight change in the color tone, the printing part can be read.
    [790] The fog is difficult to read due to the fog.
    [791] X ~ Due to severe fog, the printing part cannot be read.
    [792] Example 24
    [793] While stirring 31.5 g of 2,4-toluene diisocyanate at 60 ° C, a diluent of 21.5 g of 4,4'-diaminodiphenyl sulfone using 120 mL of methyl ethyl ketone was added dropwise thereto over 4 hours, and the reaction was carried out at 60 ° C. It continued for 2 hours at ℃. After the completion of the reaction, the reaction solution was cooled to room temperature, toluene was added thereto, and the precipitated white solid was collected by filtration, washed with toluene, and then vacuum dried overnight to obtain 47 g of a compound as white crystals. Subsequently, 9.5 g of phenol and 95 mL of methyl ethyl ketone were added to 30 g of the obtained compound, and then 30 mg of triethylamine was added thereto, and the reaction was carried out at 25 ° C. for 4 hours. After completion of the reaction, toluene was added to the reaction solution, and the precipitated crystals were collected by filtration, washed with toluene, and then vacuum dried overnight to obtain 38.5 g of the compound as white crystals. IR measurements of the white crystals were performed to find that characteristic peaks appeared at 990 cm −1 , 1110 cm −1 , 1320 cm −1 , 1590 cm −1 , 1700 cm −1, and 3350 cm −1 .
    [794] Subsequently, 2 g of the obtained compound was ground and dispersed for 6 hours in a paint shaker with 8 g of 2.5 wt% poly (vinyl alcohol) aqueous solution to prepare a dispersion. The temperature of the dispersion liquid immediately after the dispersion operation was 25 ° C. The diameter of the dispersed particles of the compound was about 0.6 μm.
    [795] Sand grinder with 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane together with 130 g of an aqueous solution of 5.4 wt% hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) Another dispersion was prepared by grinding and dispersing (manufactured by AIMEX CO., LTD .; tube volume 400 mL) at a rotation speed of 2000 rpm for 3 hours.
    [796] In addition, 70 g of diphenylsulfone was crushed and dispersed in a sand grinder (manufactured by AIMEX CO., LTD .; pipe volume: 400 mL) with a rotation speed of 2000 rpm for 3 hours with 130 g of an aqueous 8% by weight poly (vinyl alcohol) solution. A dispersion was prepared.
    [797] In addition, another dispersion was prepared by mixing 10 g of calcium carbonate and 30 g of water and stirring the mixture using a stirrer.
    [798] The dispersion and the other components were stirred and mixed in the following proportions (dry basis ratio) to obtain a coating solution: 20 parts by weight of a dry solid of the dispersion of the compound, 3-dibutylamino-6-methyl-7-anilinofluor 10 parts by weight of the dry solids of the column dispersion, 25 parts by weight of the dry solids of the diphenyl sulfone dispersion, 40 parts by weight of the dry solids of the calcium carbonate dispersion, 20 parts by weight of the dry solids of the zinc stearate dispersion (solid content of 16% by weight), And 15 parts by weight of dry solids of 15% by weight of poly (vinyl alcohol).
    [799] The coating solution was applied onto a base paper having a reference weight of 50 g / m 2 using the bar coater of No. 10. The coating amount of the coating liquid was 5 g / m 2 in dry weight. After drying, supercalendering was performed to obtain a thermal recording material.
    [800] The sensitivity evaluation result of the obtained thermal recording material was favorable with optical density 1.3. Print preservation evaluated using vinyl chloride wrap film was good. Originally, the whiteness of the surface of the recording material was about 82. The evaluation results are summarized in Table 2.
    [801] Examples 25 and 26
    [802] 3-diethylamino-6-methyl-7-anilinofluorane (Example 25) or 3,3-bis (p-dimethylamino instead of 3-dibutylamino-6-methyl-7-anilinofluorane A thermal recording material was produced and evaluated in the same manner as in Example 24 except that phenyl) -6-dimethylaminophthalide (Example 26) was used. The results obtained are summarized in Table 2.
    [803] Examples 27-29
    [804] Instead of hydroxypropylmethyl cellulose used in Example 24 to disperse 3-dibutylamino-6-methyl-7-anilinofluorane, methyl cellulose (Metlose M-15, Shin-Etsu Chemical Co., Ltd. Preparation) (Example 27), polyoxyethylene alkyl ether sulfate (Rebenol WX, manufactured by Kao Corp.) (Example 28) or sodium 2-ethylhexylsulfosuccinate (Neocol SWC, Dai-ichi Kogyo Seiyaku Co. , Ltd. (Example 29) was used, and a thermal recording material was produced in the same manner as in Example 24, and the thermal recording material was evaluated. The results obtained are summarized in Table 2.
    [805] Example 30
    [806] In the same manner as in Example 24, a urea-urethane compound developer dispersion, 3-dibutylamino-6-methyl-7-anilinofluorane dispersion, diphenyl sulfone dispersion, and calcium carbonate dispersion were prepared.
    [807] On the other hand, 70 g of 2,2-bis (4-hydroxyphenyl) propane, together with 130 g of a 5.4 wt% poly (vinyl alcohol) aqueous solution, was used at a sand grinder (manufactured by AIMEX CO., LTD .; pipe volume 400 mL) at 2000 rpm. The dispersion was prepared by grinding and dispersing for 3 hours at a rotational speed.
    [808] The dispersion and the other components were stirred and mixed in the following proportions (dry basis ratio) to obtain a coating solution: 10 parts by weight of the dry solids of the urea-urethane compound dispersion, 3-dibutylamino-6-methyl-7-anyl 10 parts by weight of the dry solids of the linofluorane dispersion, 20 parts by weight of the dry solids of the diphenyl sulfone dispersion, 10 parts by weight of the dry solids of the 2,2-bis (4-hydroxyphenyl) propane dispersion, and dry solids of the calcium carbonate dispersion 20 parts by weight, 10 parts by weight of dry solids of zinc stearate dispersion (solid content of 16% by weight), and 10 parts by weight of dry solids of 15% by weight of poly (vinyl alcohol).
    [809] A thermal recording material was produced and evaluated in the same manner as in Example 24 except that the coating liquid obtained above was used. The results obtained are summarized in Table 2.
    [810] Examples 31 to 34
    [811] 4-isopropyloxyphenyl-4'-hydroxyphenyl sulfone (D-8, trade name, manufactured by Nippon Soda Co., Ltd.) instead of 2,2-bis (4-hydroxyphenyl) propane (Example 31) , Bis (3-allyl-4-hydroxyphenyl) sulfone (TG-SA, trade name, manufactured by Nippon Kayaku Co., Ltd.) (Example 32), 2,4'-dihydroxydiphenyl sulfone (24BPS, Trade name, manufactured by Nicca Chemical Co., Ltd. (Example 33), or 4,4 '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol (D-90, trade name, Nippon soda Co. , A thermal recording material was produced and evaluated in the same manner as in Example 30, except that a mixture (Example 34) having a main component as a main component was used. The results obtained are summarized in Table 2.
    [812] Examples 35-64
    [813] Instead of diphenyl sulfone, β-naphthylbenzyl ether (BON, trade name, manufactured by Ueno Fine Chemicals Industry Ltd.) (Examples 35 to 39), p-benzylbiphenyl (PBBP, trade name, Nippon Steel Chemical Co., Ltd. Preparation) (Examples 40 to 44), 1,2-di (m-methylphenoxy) ethane (KS-235, trade name, manufactured by SANKOSHA CO., LTD.) (Examples 45 to 49), di-p- Methylbenzyl oxalate (HS3520, trade name, manufactured by Dainippon Ink and Chemicals, Inc.) (Examples 50-54), 1,2-diphenoxymethylbenzene (PMB-2, trade name, manufactured by Nicca Chemical Co., Ltd.) Each of Examples 30-34, except that (Examples 55-59) or m-terphenyl (mtp, trade name, manufactured by Nippon Steel Chemical Co., Ltd.) (Examples 60-64) were used. A thermal recording material was produced in the same manner as in, and the thermal recording material was evaluated. The results obtained are summarized in Table 2.
    [814] Examples 65 and 66
    [815] Instead of diphenyl sulfone, stearamide emulsified products (Highmicron G-270, trade name, manufactured by Chukyo Yushi Co., Ltd.) (Example 65) or o-chloroanilide (manufactured by Mitsuboshi Chemical Co., Ltd.) (Example 66 ), And the thermal recording material was produced and evaluated in the same manner as in Example 24. The results obtained are summarized in Table 2.
    [816] Example 67
    [817] Except for adding a stilbene-based fluorescent dye (Kayahol 3BS, trade name, manufactured by Nippon Kayaku Co., Ltd.) to the coating solution prepared in Example 30 at a ratio of 1 part by weight per 100 parts by weight (dry solid) of the coating solution. In the same manner as in Example 30, a thermal recording material was produced and evaluated. The results obtained are summarized in Table 2.
    [818] Example 68
    [819] 70 g of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, together with 130 g of a 5.4 wt% poly (vinyl alcohol) aqueous solution A dispersion liquid was prepared by pulverizing and dispersing for 3 hours at a rotation speed of 2000 rpm in a tube volume of 400 mL).
    [820] Subsequently, the 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane dispersion was added to the coating solution prepared in Example 30 per 100 parts by weight of the coating solution (dry solid). A thermal recording material was produced and evaluated in the same manner as in Example 30 except that the amount was added at a ratio of 10 parts by weight. The results obtained are summarized in Table 2.
    [821] Example 69
    [822] After adding 30 g of toluene as a solvent to 30 g of 2, 4- toluene diisocyanate, 3.24 g of phenols were added here, and the said reaction was performed at 100 degreeC for 1 hour 30 minutes. After the completion of the reaction, toluene was concentrated and removed, hexane was added to the residue, and the precipitated white solid was collected by filtration, washed with hexane, and then dried in vacuo overnight to give 6.9 g of a compound as white crystals. Then, to 5.0 g of the obtained compound, 100 g of toluene was added as a solvent, followed by 3.50 g of aniline, and the reaction was carried out at 25 ° C. for 3 hours. The precipitated crystals were collected by filtration, washed with hexane and dried in vacuo overnight to give 5.5 g of the compound as white crystals. IR measurements of the white crystals were performed to find that characteristic peaks appeared at 890 cm −1 , 1000 cm −1 , 1030 cm −1 , 1440 cm −1 , 1720 cm −1, and 3350 cm −1 .
    [823] Subsequently, a thermal recording material was produced and evaluated in the same manner as in Example 68 except for using the obtained compound instead of the urea-urethane compound used in Example 68. The results obtained are summarized in Table 2.
    [824] Examples 70-75
    [825] 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) instead of 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane Butane (Adecaarcles DH-43, manufactured by Asahi Denka Kogyo KK) (Example 70), 4-benzyloxy-4 '-(2,3-epoxy-2-methylprop-1-yloxy) diphenyl sulfone (NTZ -95, manufactured by Nippon Soda Co., Ltd. (Example 71), methylenebis (2-hydroxy-3- (benzotriazol-2-yl) -5-tert-octylphenyl) (Example 72) , 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (Adecaarcles DN-13, manufactured by Asahi Denka Kogyo KK) (Example 73), 1,3,5-tris (2,6-dimethyl- 4-tert-butyl-3-hydroxybenzyl) isocyanurate (Adecaarcles DH-48, manufactured by Asahi Denka Kogyo KK) (Example 74) or sodium 2,2-methylenebis (4,6-di-tert- A thermal recording material was produced in the same manner as in Example 68, except that butylphenyl) phosphate (Adecaarcles F-85, manufactured by Asahi Denka Kogyo KK) (Example 75) was used, and the thermal It was rated the rock material. The results obtained are summarized in Table 2.
    [826] Comparative Example 8
    [827] A thermal recording material was produced and evaluated in the same manner as in Example 24, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound synthesized in Example 24. . The results obtained are summarized in Table 2.
    [828]
    [829]
    [830] 1. The sensitivity increases with increasing optical density (OD value).
    [831] 2. Plasticizer resistance (print preservation)
    [832] ◎-It does not fade substantially.
    [833] There is slight change in hue, but there is no scratch.
    [834] Discoloration markedly.
    [835] X ~ The color tone of printing disappears completely.
    [836] 3. The higher the value, the higher the whiteness. If the value is 80 or more, the whiteness is practically sufficient.
    [837] [Friction resistance]
    [838] The surface of the thermal recording material is rubbed strongly with a fingernail, and it is visually determined whether the rubbed portion is colored. If the recording material does not show noticeable signs of friction, it is evaluated to have good friction resistance.
    [839] [Accumulation of friction traces]
    [840] A cylinder having a diameter of 5 cm (weight: 2 kg) was moved 50 times on the same surface of length 20 cm at a speed of 20 cm / sec on the recording surface of each manufactured thermal recording material, and then the recording material was left at room temperature for 1 week. Let's do it. After one week of standing, the readability of the printed image is visually determined. If the print image is sufficiently readable, the recording material is evaluated as good.
    [841] Example 76
    [842] A thermal coating solution was obtained in the same manner as in Example 24. Subsequently, the coating liquid was applied onto a base paper having a reference weight of 50 g / m 2 using the bar coater of No. 10. After drying, supercalendering was performed to form a thermochromic layer on the support. The coating amount of the coating liquid was 5 g / m 2 in dry weight.
    [843] Subsequently, a dispersion liquid was prepared by pulverizing and dispersing 40 g of kaolin with 60 g of an aqueous 0.7% sodium hexametaphosphate solution at a rotation speed of 2000 rpm for 3 hours in a sand grinder (manufactured by AIMEX CO., LTD .; pipe volume 400 mL).
    [844] The kaolin dispersion and other components were stirred and mixed in the following proportions (dry basis ratio) to obtain a coating liquid for forming a protective layer: 20 parts by weight of the dry solids of the kaolin dispersion and a zinc stearate dispersion (solids content of 16% by weight). 10 parts by weight of the dry solids, 40 parts by weight of the dry carboxy-modified poly (vinyl alcohol) aqueous solution, and 5 parts by weight of the dry solids of the polyacrylamido epichlorohydrin crosslinking agent solution.
    [845] The coating liquid for protective layer formation was apply | coated on the thermal coloring layer using the bar coater of No.5. After drying, supercalendering was performed to obtain a thermal recording material. The coating amount of the coating liquid for protective layer formation was 2 g / m <2> by dry weight.
    [846] The sensitivity evaluation result of the obtained thermal recording material was favorable with optical density 1.3. Print preservation evaluated using vinyl chloride wrap film was good. The surface of the thermal recording material was rubbed strongly with a fingernail and visually judged whether the rubbing portion was colored, and it was found that no noticeable friction was found, that is, the friction resistance was good. The result of the long time test for evaluating the friction resistance was good that the printed image was sufficiently readable. The evaluation results are summarized in Table 3.
    [847] Examples 77 and 78
    [848] A thermal recording material was prepared in the same manner as in Example 76 except for using poly (vinyl alcohol) (Example 77) or acrylic acid copolymer (Example 78) instead of carboxy modified poly (vinyl alcohol). . The results obtained are summarized in Table 3.
    [849] Examples 79-81
    [850] In the same manner as in Example 76, except for using aluminum hydroxide (Example 79), crosslinkable poly (methyl methacrylate) resin (Example 80) or silicon dioxide (Example 81) instead of kaolin The thermal recording material was manufactured. The results obtained are summarized in Table 3.
    [851] Example 82
    [852] A 33 wt% calcined kaolin dispersion and a 50 wt% styrene / butadiene based latex aqueous dispersion were stirred and mixed at a ratio of 100 parts by weight and 12 parts by weight (dry basis ratio), respectively, to obtain a coating solution for an interlayer.
    [853] Subsequently, 20 weight% acrylic acid emulsion and 10 weight% silica fine powder dispersion (Fineseal SP-10) were stirred and mixed at a ratio of 100 parts by weight and 7 parts by weight, respectively, to obtain a back coating liquid.
    [854] On one side of the base paper (50 g / m 2 ), the above coating solution for the intermediate layer was applied in solids in an amount of 10 g / m 2 and dried, and the thermal coating liquid prepared in Example 76 was used as a solid on the same side. After coating and drying in an amount of g / m 2 , the coating liquid for protective layer prepared in Example 76 was applied in the amount of 2 g / m 2 as a solid on the same side and dried. Subsequently, the back coating liquid was applied to the uncoated side in solids in an amount of 1 g / m 2 , dried, and calendered to prepare a thermal recording material and to evaluate it. The results obtained are summarized in Table 3.
    [855] Comparative Example 9
    [856] A thermal recording material was produced in the same manner as in Example 76 except that no coating liquid for protective layer formation was applied on the thermal color developing layer, and the recording material was evaluated. The results obtained are summarized in Table 3.
    [857]
    [858] 1. The sensitivity increases with increasing optical density (OD value).
    [859] 2. Plasticizer resistance (print preservation)
    [860] ◎-It does not fade substantially.
    [861] There is slight change in hue, but there is no scratch.
    [862] Discoloration markedly.
    [863] X ~ The color tone of printing disappears completely.
    [864] 3. Friction resistance
    [865] ◎-No trace of friction develops black color.
    [866] Friction marks show slight color development, but not remarkable
    [867] Friction marks show color development and are remarkable.
    [868] X ~ A trace of friction develops black color and is remarkable.
    [869] 4. Accumulation of Friction Traces
    [870] Good results are obtained without difficulty in reading the print image.
    [871] Although the traces of friction show slight color development, the printed image is sufficiently readable.
    [872] Since the trace of friction shows color development, it is difficult to read the printed image.
    [873] Since the frictional marks develop black, the print image cannot be read.
    [874] Example 83
    [875] 2 g of the compound obtained in Example 24 was pulverized and dispersed in a paint shaker for 6 hours with 8 g of 2.5 wt% poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) A dispersion was prepared. The temperature of the dispersion liquid immediately after the dispersion operation was 25 ° C., and the pH of the dispersion liquid was 8. The diameter of the dispersed particles of the compound was 0.6 µm.
    [876] 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane together with 130 g of a 5.4 wt% poly (vinyl alcohol) aqueous solution was added at 2000 rpm in a sand grinder (manufactured by AIMEX CO., LTD .; tube volume 400 mL). Another dispersion was prepared by grinding and dispersing for 3 hours at rotational speed.
    [877] In addition, sand grinder (manufactured by AIMEX CO., LTD.) With 70 g of diphenylsulfone with 130 g of an aqueous solution of 5.4 wt% poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.); 400 mL) was ground and dispersed for 3 hours at a rotational speed of 2000 rpm to prepare another dispersion.
    [878] In addition, 10 g of calcium carbonate and 30 g of water were mixed, and another dispersion was obtained by stirring the mixture using a stirrer.
    [879] The dispersion and the other components were stirred and mixed in the following proportions (dry reference ratio) to obtain a coating solution: 30 parts by weight of a dry solid of the dispersion of the compound, 3-dibutylamino-6-methyl-7-anilinofluoro 15 parts by weight of the dry solids of the column dispersion, 30 parts by weight of the dry solids of the diphenyl sulfone dispersion, 20 parts by weight of the dry solids of the calcium carbonate dispersion, 10 parts by weight of the dry solids of the zinc stearate dispersion (solid content of 16% by weight), And 7 parts by weight of dry solids of 15% by weight of poly (vinyl alcohol). PH of the coating liquid was 8.2.
    [880] Subsequently, the coating solution was applied on the surface of the quality paper having a reference weight of 50 g / m 2 in an amount of 5 g / m 2 as a dry weight and dried, followed by supercalendering to prepare a thermal recording material. The color sensitivity evaluation results of the obtained thermal recording material were good at an optical density of 1.3. The print retention evaluated using the vinyl chloride wrap film was so good that no fading occurred. The results obtained are summarized in Table 4.
    [881] Example 84
    [882] 2 g of the same urea-urethane compound and 2 g of diphenyl sulfone as used in Example 83, together with 16 g of 2.5% by weight aqueous solution of modified poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), The dispersion was prepared by grinding and dispersing for 6 hours in a paint shaker.
    [883] Then, in place of the urea-urethane compound dispersion and the diphenyl sulfone dispersion used in Example 83, the thermosensitive recording material was prepared in the same manner as in Example 83 except that the co-dispersion was added in a proportion of 60 parts by weight as a dry solid. Was prepared and the recording material was evaluated. The results obtained are summarized in Table 4.
    [884] Example 85
    [885] To 61 g of 2,4-toluene diisocyanate, 450 g of toluene was added as a solvent, and a solution of 26 g of aniline in 150 g of toluene was added dropwise over 6 hours, and the reaction was carried out at 5 ° C. for 7 hours. After the completion of the reaction, the precipitated white solid was collected by filtration, washed with toluene, and then vacuum dried overnight to obtain 70 g of the compound as white crystals. Then, to 30 g of the obtained compound, 365 g of toluene was added as a solvent, followed by 12.2 g of 2,2-bis (4-hydroxyphenyl) propane and 0.3 mg of triethylamine, and the reaction was carried out at 60 ° C. For 4 hours at 70 ° C. for 3 hours and then at 80 ° C. for 3 hours with stirring. After the completion of the reaction, the reaction solution was cooled to room temperature, and the precipitated crystals were collected by filtration, washed with toluene, and then vacuum dried overnight to give 42 g of a compound as white crystals. IR measurements of the white crystals were performed, indicating that characteristic peaks appeared at 750 cm −1 , 840 cm −1 , 1020 cm −1 , 1500 cm −1 , 1600 cm −1 , 1720 cm −1, and 3320 cm −1 Found that.
    [886] 2 g of the compound and 2 g of diphenyl sulfone, together with 16 g of 2.5% by weight modified poly (vinyl alcohol) (Gohseran L-3266, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) aqueous solution, were ground in a paint shaker for 6 hours, Dispersion was made.
    [887] Subsequently, instead of the urea-urethane compound dispersion and the diphenyl sulfone dispersion used in Example 83, a co-dispersion of the compound and diphenyl sulfone was added in a proportion of 60 parts by weight as a dry solid, and In the same manner, a thermal recording material was produced and the recording material was evaluated. The results obtained are summarized in Table 4.
    [888] Example 86
    [889] 2 g of the compound obtained in Example 69 and 2 g of dimethylbenzyl oxalate, together with an aqueous solution of 2.5% by weight modified poly (vinyl alcohol) (Gohseran L-3266, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) in a paint shaker The dispersion was prepared by grinding and dispersing for 6 hours.
    [890] Subsequently, in place of the urea-urethane compound dispersion and the diphenyl sulfone dispersion used in Example 83, except that a co-dispersion of the compound and dimethylbenzyl oxalate was added in a proportion of 60 parts by weight as a dry solid, A thermal recording material was produced in the same manner as, and the recording material was evaluated. The results obtained are summarized in Table 4.
    [891] Example 87
    [892] 2 g of the compound obtained in Example 2 was pulverized and dispersed for 6 hours in a paint shaker, together with 8 g of an aqueous 2.5% by weight methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) solution. Manufactured.
    [893] Subsequently, a thermal recording material was produced in the same manner as in Example 83 except that the dispersion of the compound was used instead of the urea-urethane compound dispersion used in Example 83, and the recording material was evaluated. The results obtained are summarized in Table 4.
    [894] Examples 88-92
    [895] Instead of poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as dispersant for the urea-urethane compound in Example 83, polycarboxylic acid ammonium salt (Dispersant 5027, Sunnopco Co ., Ltd.) (Example 88), Water-soluble low molecular weight copolymer (Discort N14, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (Example 89), Sodium 2-ethylhexylsulfosuccinate (Neocol SWC, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (Example 90), hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (Example 91), or condensation A thermal recording material was produced in the same manner as in Example 83 except that sodium naphthalene sulfonate (manufactured by Roma D, Sunnopco Co., Ltd.) (Example 92) was used, and the thermal recording material was evaluated. . The results obtained are summarized in Table 4.
    [896] Examples 93-98
    [897] Instead of poly (vinyl alcohol) (Gosenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as dispersant for diphenyl sulfone in Example 83, methylcellulose (Metlose SM-15, Shin-Etsu Chemical Co.) ., Ltd.) (Example 93), water-soluble low molecular weight copolymer (Discort N14, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) (Example 94), sodium 2-ethylhexylsulfosuccinate (Neocol SWC, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. (Example 95), hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (Example 96), condensed sodium Except using naphthalene sulfonate (Roma D, manufactured by Sunnopco Co., Ltd.) (Example 97) or polycarboxylic acid ammonium salt (Dispersant 5027, manufactured by Sunnopco Co., Ltd.) (Example 98) Manufactured the thermal recording material in the same manner as in Example 83, and evaluated the thermal recording material. The results obtained are summarized in Table 4.
    [898] Examples 99-101
    [899] Instead of poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as dispersant for diphenyl sulfone in Example 87, methyl cellulose (Metlose SM-15, Shin-Etsu Chemical Co.) , Ltd.) (Example 99), hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (Example 100) or modified poly (vinyl alcohol) (Gohseran L- A thermal recording material was produced in the same manner as in Example 87 except that 3266, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) (Example 101), and the thermal recording material was evaluated. The results obtained are summarized in Table 4.
    [900] Example 102
    [901] Instead of methyl cellulose (Metlose SM-15, manufactured by Shin-Etsu Chemical Co., Ltd.) used as a dispersant for the urea-urethane compound in Example 99, modified poly (vinyl alcohol) (Gohseran L-3266, Nippon Synthetic Chemical) Except for using Industry Co., Ltd.), a thermal recording material was produced in the same manner as in Example 99, and the recording material was evaluated. The results obtained are summarized in Table 4.
    [902] Examples 103 and 104
    [903] Instead of poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as dispersant for diphenyl sulfone in Example 89, methyl cellulose (Metlose SM-15, Shin-Etsu Chemical Co.) Example 89, except that hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (Example 104) was used. A thermal recording material was produced in the same manner as, and the thermal recording material was evaluated. The results obtained are summarized in Table 4.
    [904] Examples 105-106
    [905] Instead of poly (vinyl alcohol) (Gohsenol KL-05, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) used as dispersant for diphenyl sulfone in Example 91, methyl cellulose (Metlose SM-15, Shin-Etsu Chemical Co.) Example 91, except that hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) (Example 106) was used. A thermal recording material was produced in the same manner as, and the thermal recording material was evaluated. The results obtained are summarized in Table 4.
    [906] Examples 107 and 108
    [907] Instead of poly (vinyl alcohol) used as dispersant for 3-dibutylamino-6-methyl-7-anilinofluorane in Example 104, hydroxypropylmethyl cellulose (Metlose 60SH-03, Shin-Etsu Chemical Co. , Ltd.) (Example 107), or hydroxypropylmethyl cellulose (Metlose 60SH-03, manufactured by Shin-Etsu Chemical Co., Ltd.) and sodium 2-ethylhexylsulfosuccinate (Neocol SWC, Dai- A thermal recording material was produced in the same manner as in Example 104, except that a mixed dispersant (weight ratio 1/1) (Example 108) of ichi Kogyo Seiyaku Co., Ltd. was used, and the thermal recording was performed. The material was evaluated. The results obtained are summarized in Table 4.
    [908] Comparative Example 10
    [909] A thermal recording sheet was produced and evaluated in the same manner as in Example 83 except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound used in Example 83. The results obtained are summarized in Table 4.
    [910] Comparative Examples 11 and 12
    [911] Except for changing the dispersion time, the same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83, and the average particle size of the obtained dispersion was measured to obtain 0.04 μm (Comparative Example). 11) and 6.5 μm (Comparative Example 12). A thermal recording sheet was produced and evaluated in the same manner as in Example 83 except that each of the above dispersion liquids was used. The results obtained are summarized in Table 4.
    [912] Comparative Example 13
    [913] The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83 except that the dispersion temperature was maintained at 65 ° C. during the dispersion operation. A thermal recording sheet was produced and evaluated in the same manner as in Example 83 except that the obtained dispersion was used. The results obtained are summarized in Table 4.
    [914] Comparative Example 14
    [915] The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83 except that the pH of the dispersion medium used for the dispersion operation was adjusted to 4. A thermal recording sheet was produced and evaluated in the same manner as used in Example 83 except that the dispersion obtained above was used. The results obtained are summarized in Table 4.
    [916] Comparative Example 15
    [917] The same urea-urethane compound as used in Example 83 was dispersed in the same manner as in Example 83, except that the pH of the dispersion medium used for the dispersion operation was adjusted to 11. A thermal recording sheet was produced and evaluated in the same manner as used in Example 83 except that the dispersion obtained above was used. The results obtained are summarized in Table 4.
    [918] Comparative Example 16
    [919] The pH of the coating liquid prepared in Example 83 was adjusted to 4.0 using 1N sulfuric acid. A thermal recording sheet was produced and evaluated in the same manner as in Example 83 except that the above adjusted coating liquid was used. The results obtained are summarized in Table 4.
    [920] Comparative Example 17
    [921] The pH of the coating solution prepared in Example 83 was adjusted to 12.5 using 1N sodium hydroxide. A thermal recording sheet was produced and evaluated in the same manner as used in Example 83 except that the above adjusted coating liquid was used. The results obtained are summarized in Table 4.
    [922]
    [923] 1. The sensitivity increases with increasing optical density (OD value).
    [924] 2. Plasticizer resistance (print preservation)
    [925] ◎-It does not fade substantially.
    [926] There is slight change in hue, but there is no scratch.
    [927] Discoloration markedly.
    [928] X ~ The color tone of printing disappears completely.
    [929] 3. Plasticizer resistance (retention of surface of original recording material)
    [930] The original recording material surface is hardly colored.
    [931] There is a subtle color change, but the original recording material surface is very weakly colored.
    [932] -The original recording material surface is markedly colored.
    [933] The original recording material surface is colored so badly that printing is difficult to read.
    [934] Example 109
    [935] The coating liquid prepared in Example 83 was applied on the surface of the quality paper with a surface pH of 3.2 in an amount of 5 g / m 2 by dry weight, dried, and then subjected to supercalendering to prepare a thermal recording material. The color sensitivity evaluation results of the obtained thermal recording material were good at an optical density of 1.3. The print retention evaluated using the vinyl chloride wrap film was so good that no fading occurred. Originally, the retention of the recording material surface was so good that the surface was hardly colored. The results obtained are summarized in Table 5.
    [936] Examples 110 and 111
    [937] Heat-sensitive in the same manner as in Example 109, except that instead of using a high-quality paper having a surface pH of 3.2 (Example 110) or a high-quality paper having a surface pH of 6.8 (Example 111). The recording material was produced and evaluated. The results obtained are summarized in Table 5.
    [938] Comparative Examples 18 and 19
    [939] Heat-sensitive in the same manner as in Example 109, except that instead of using a paper having a surface pH of 3.2, a paper having a surface pH of 2.8 (Comparative Example 18) or a paper having a surface pH of 9.5 (Comparative Example 19). The recording material was produced and evaluated. The results obtained are summarized in Table 5.
    [940]
    [941] 1. The sensitivity increases with increasing optical density (OD value).
    [942] 2. Plasticizer resistance (print preservation)
    [943] ◎-It does not fade substantially.
    [944] There is slight change in hue, but there is no scratch.
    [945] Discoloration markedly.
    [946] X ~ The color tone of printing disappears completely.
    [947] 3. Plasticizer resistance (retention of surface of original recording material)
    [948] The original recording material surface is hardly colored.
    [949] There is a subtle color change, but the original recording material surface is very weakly colored.
    [950] -The original recording material surface is markedly colored.
    [951] The original recording material surface is colored so badly that printing is difficult to read.
    [952] Example 112
    [953] A) Preparation of Coating Liquid for Magnetic Recording Layer
    [954] 100 parts by weight of barium ferrite (magnetic force 2700), 25 parts by weight sodium polyacrylate (20% by weight aqueous solution), 100 parts by weight of poly (vinylidene chloride) (49% by weight dispersion), 15 parts by weight carbon black (36% by weight dispersion) 10 parts by weight of paraffin wax (20% by weight dispersion obtained using methyl cellulose) and 100 parts by weight of water were dispersed in a ball mill for 10 hours to prepare a coating liquid for a magnetic recording layer.
    [955] B) Preparation of Coating Liquid for Thermal Recording Layer
    [956] In the same manner as in Example 24, a coating liquid for a thermal recording layer was obtained.
    [957] Then, the coating liquid for magnetic recording layer prepared in A) was applied to one side of the good-quality paper having a reference weight of 150 g / m 2 in an amount of 30 g / m 2 in dry weight, and dried to apply the magnetic recording layer. Obtained. Subsequently, the coating liquid for thermally sensitive recording layer prepared in B) was applied to the other side of the support having the magnetic recording layer in an amount of 6 g / m 2 by dry weight, dried, and then super-calendered to heat A magnetic recording material was obtained.
    [958] The color sensitivity evaluation results of the thermal recording layer of the obtained thermal magnetic recording material were satisfactory at an optical density of 1.3. Print preservation evaluated using vinyl chloride wrap film was so good that little fading occurred. The results obtained are summarized in Table 6.
    [959] Example 113
    [960] C) Preparation of Coating Liquid for Protective Layer
    [961] 20 parts by weight of zinc stearate, 20 parts by weight of a 5% by weight aqueous solution of methyl cellulose and 60 parts by weight of water were mixed and then dispersed in a sand grinder for 2 hours. Subsequently, 20 parts by weight of a 10% by weight carboxy-modified poly (vinyl alcohol) aqueous solution, 1.5 parts by weight of silica, 6.5 parts by weight of 12.5% by weight polyamido epichlorohydrin aqueous solution and 15.0 parts by weight of water were mixed, followed by 2 hours in a sand grinder. Dispersed during.
    [962] Subsequently, 0.7 parts by weight of the obtained zinc stearate dispersion, 45.0 parts by weight of the obtained silica dispersion, and 11.3 parts by weight of water were mixed to prepare a coating liquid for protective layer. Except that a protective layer was formed by applying the above-mentioned coating liquid for protective layers in an amount of 3 g / m 2 by dry weight on the thermal recording layer of the thermal magnetic recording material of Example 112 and then drying to form a protective layer. A thermal magnetic recording material was produced in the same manner as 112, and the thermal magnetic recording material was evaluated. The results obtained are summarized in Table 6.
    [963] Example 114
    [964] D) Preparation of Coating Liquid for Interlayers
    [965] A coating liquid for an intermediate layer consisting of 80 parts by weight of a 48% polystyrene fine particle dispersion (dry solids) and 20 parts by weight of a 40% styrene-acrylic acid ester copolymer emulsion (dry solids) was prepared.
    [966] Example 113 and the difference between the thermal recording layer of the thermosensitive magnetic recording material of Example 113 and the support, except that the coating liquid was applied in an amount of 8 g / m 2 by dry weight and then dried to form an intermediate layer. A thermal magnetic recording material was produced in the same manner, and the thermal magnetic recording material was evaluated. The results obtained are summarized in Table 6.
    [967] Comparative Example 20
    [968] A thermal recording sheet was produced and evaluated in the same manner as in Example 112, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound used in Example 112. The results obtained are summarized in Table 6.
    [969]
    [970] 1. The sensitivity increases with increasing optical density (OD value).
    [971] 2. Plasticizer resistance (print preservation)
    [972] ◎-It does not fade substantially.
    [973] There is slight change in hue, but there is no scratch.
    [974] Discoloration markedly.
    [975] X ~ The color tone of printing disappears completely.
    [976] Example 115
    [977] A) Preparation of Coating Liquid for Thermal Recording Layer
    [978] In the same manner as in Example 24, a coating liquid for a thermal recording layer was prepared.
    [979] On the surface of the quality paper having a reference weight of 150 g / m 2, the coating liquid for thermal recording layer prepared in A) was applied in an amount of 7 g / m 2 in dry weight, dried, and super-calendered to heat A sheet coated with a recording layer was prepared.
    [980] B) Preparation of Release Sheet
    [981] On a base paper having a reference weight of 40 g / m 2 , a release agent composed of oily dimethyl silicone was applied in an amount of 1 g / m 2 using a gravure coater to form a release layer. Subsequently, the pressure-sensitive adhesive layer component composed of 100 parts by weight of chlorinated rubber, 20 parts by weight of ester gum and 120 parts by weight of dibutyl phthalate was applied on the release layer in an amount of 10 g / m 2 .
    [982] C) Preparation of labels for thermal recording
    [983] A label for thermal recording was prepared by pasting the uncoated side of the sheet coated with the thermal recording layer prepared in paragraph A) and the side coated with the adhesive layer of the release sheet prepared in paragraph B) to face each other. did.
    [984] The evaluation result of the color development sensitivity of the obtained thermal recording label was good at an optical density of 1.3. The print retention evaluated using the vinyl chloride wrap film was so good that no fading occurred. The results obtained are summarized in Table 7.
    [985] Example 116
    [986] D) Preparation of coating liquid for back coating layer
    [987] By coating 100 parts by weight of the styrene-maleic acid copolymer and 50 parts by weight of kaolin, a coating liquid for a back coating layer was prepared. Except for forming the back coating layer by coating the coating liquid in an amount of 1 g / m 2 on a dry weight on the opposite side of the surface coated with the thermal recording layer of the thermal recording label of Example 115, followed by drying. In the same manner as in Example 115, a label for thermal recording was produced, and the label was evaluated. The results obtained are summarized in Table 7.
    [988] Example 117
    [989] E) Preparation of Coating Liquid for Interlayers
    [990] A coating liquid for an intermediate layer consisting of 80 parts by weight of a 48% polystyrene fine particle dispersion (dry solids) and 20 parts by weight of a 40% styrene-acrylic acid ester copolymer emulsion (dry solids) was prepared.
    [991] Example 116 and Example 116 except that the coating liquid was applied in an amount of 8 g / m 2 by dry weight between the thermal recording layer and the support of the thermal recording label of Example 116, followed by drying to form an intermediate layer. A label for thermal recording was prepared in the same manner and the label was evaluated. The results obtained are summarized in Table 7.
    [992] Example 118
    [993] F) Preparation of Coating Liquid for Protective Layer
    [994] 20 parts by weight of zinc stearate, 20 parts by weight of a 5% by weight aqueous solution of methyl cellulose and 60 parts by weight of water were mixed and then dispersed in a sand grinder for 2 hours. Subsequently, 20 parts by weight of a 10% by weight carboxy-modified poly (vinyl alcohol) aqueous solution, 1.5 parts by weight of silica, 6.5 parts by weight of 12.5% by weight polyamido epichlorohydrin aqueous solution and 15.0 parts by weight of water were mixed, followed by 2 hours in a sand grinder. Dispersed during.
    [995] Subsequently, 0.7 parts by weight of the obtained zinc stearate dispersion, 45.0 parts by weight of the obtained silica dispersion, and 11.3 parts by weight of water were mixed to prepare a coating liquid for protective layer. On the thermal recording layer of the thermal recording label of Example 117, the coating liquid was applied in an amount of 3 g / m 2 by dry weight, and then dried to form a protective layer, which was the same as that of Example 117. A label for thermal recording was produced in a manner and the label was evaluated. The results obtained are summarized in Table 7.
    [996] Comparative Example 21
    [997] A thermal recording sheet was produced and evaluated in the same manner as in Example 115, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound used in Example 115. The results obtained are summarized in Table 7.
    [998]
    [999] 1. The sensitivity increases with increasing optical density (OD value).
    [1000] 2. Plasticizer resistance (print preservation)
    [1001] ◎-It does not fade substantially.
    [1002] There is slight change in hue, but there is no scratch.
    [1003] Discoloration markedly.
    [1004] X ~ The color tone of printing disappears completely.
    [1005] Example 119
    [1006] The coating material for the thermochromic layer described below and the coating material for the intermediate layer were coated on one side of a commercially available poly (ethylene terephthalate) film (Lumilar E, trade name, Toray Industries, Inc.) having a thickness of 75 μm. Apply to form in the following order:
    [1007] Cyan color-sensitive thermal recording layer, intermediate layer, magenta color-sensitive thermal recording layer, middle layer, yellow color-sensitive thermal recording layer and intermediate layer. The coating amount of each thermal recording layer and each intermediate layer after drying was applied by bar coating so as to be 6.5 g / m 2 and 2.0 g / m 2 , respectively, to obtain a multicolor thermal recording material.
    [1008] Preparation of Coating Material for Cyan Color Thermal Recording Layer
    [1009] Liquid A (thermochromic dye dispersion)
    [1010] After mixing 20 parts by weight of 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 20 parts by weight of a 10% poly (vinyl alcohol) aqueous solution and 10 parts by weight of water, sand grinder (AIMEX CO. , LTD.), And pulverized to prepare a dispersion having an average particle size of 0.7 µm.
    [1011] Liquid B (Developer Dispersion)
    [1012] A urea-urethane compound was synthesized in the same manner as in Example 24, and a dispersion was prepared by pulverizing and dispersing 30 g of the compound together with 120 g of 2.5% by weight aqueous poly (vinyl alcohol) solution in a sand grinder for 3 hours. The temperature of the dispersion liquid immediately after the said dispersion operation was 25 degreeC. The dispersed particle diameter of the compound was 0.6 mu m.
    [1013] 30 parts by weight of liquid A, 120 parts by weight of liquid B, 52 parts by weight of 60% calcium carbonate slurry, 40 parts by weight of 10% poly (vinyl alcohol) aqueous solution, SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co. , Ltd .; 28 parts by weight of solid content 50%), stearamide (Celozol A-877, trade name, manufactured by Chukyo Yushi Co., Ltd .; 11 parts by weight of solid content 26.5%) and 82 parts by weight of water to develop cyan color A coating material for the thermochromic layer was prepared.
    [1014] Preparation of Coating Material for Magenta Coloring Thermal Recording Layer
    [1015] Liquid A (thermochromic dye dispersion)
    [1016] 20 parts by weight of 4-N- (2- (2,4-di-tert-amylphenoxy) butyryl) piperazinobenzenediazonium hexafluorophosphate, 20 parts by weight of 10% poly (vinyl alcohol) aqueous solution and water After mixing 10 parts by weight, the mixture was dispersed and ground in a sand grinder to prepare a dispersion having an average particle size of 0.7 mu m.
    [1017] Liquid B (coupler dispersion)
    [1018] 50 parts by weight of 1- (2'-octylphenyl) -3-methyl-5-pyrazolone, 50 parts by weight of 1,2,3-triphenylguanidine, 50 parts by weight of 10% poly (vinyl alcohol) aqueous solution and 25 parts by weight of water After the portions were mixed, they were dispersed and pulverized in a sand grinder to prepare a dispersion liquid having an average particle diameter of 1.0 mu m.
    [1019] 30 parts by weight of liquid A, 90 parts by weight of liquid B, 52 parts by weight of 60% calcium carbonate slurry, 40 parts by weight of 10% poly (vinyl alcohol) aqueous solution, SBR latex (L-1537, trade name, ASAHI Chemical Industry, Co. , Ltd .; 28 parts by weight of solid content 50%), stearamide (Celozol A-877, trade name, manufactured by Chukyo Yushi Co., Ltd .; 11 parts by weight of solid content 26.5%) and 82 parts by weight of water to develop magenta A coating material for the thermochromic layer was prepared.
    [1020] Preparation of Coating Material for Yellow Color Thermal Recording Layer
    [1021] Liquid A (thermochromic dye dispersion)
    [1022] 20 parts by weight of 2,5-dibutoxy-4-tolylthiobenzenebenzenediazonium hexafluorophosphate, 20 parts by weight of 10% poly (vinyl alcohol) aqueous solution and 10 parts by weight of water are mixed, and then dispersed and ground in a sand grinder. And a dispersion having an average particle size of 0.7 µm were prepared.
    [1023] Liquid B (coupler dispersion)
    [1024] 50 parts by weight of 2-chloro-5- (3- (2,4-di-tert-pentyl) phenoxypropylamino) acetanilide, 50 parts by weight of 1,2,3-triphenylguanidine, 10% poly (vinyl alcohol ) 50 parts by weight of an aqueous solution and 25 parts by weight of water were mixed, and then dispersed and ground in a sand grinder to prepare a dispersion having an average particle size of 1.0 µm.
    [1025] 30 parts by weight of liquid A, 90 parts by weight of liquid B, 52 parts by weight of 60% calcium carbonate slurry, 40 parts by weight of 10% poly (vinyl alcohol) aqueous solution, SBR latex (L-1537, trade name, ASAHIChemical Industry, Co., Ltd .; solid color 50%) 28 parts by weight, stearamide (Celozol A-877, trade name, manufactured by Chukyo Yushi Co., Ltd .; 11 parts by weight of solids content 26.5%) and 82 parts by weight of water, yellowish color development The coating material for the coloring layer was prepared.
    [1026] Preparation of Coating Material for Interlayers (Solid Content: 15%)
    [1027] 60% kaolinite clay (average particle size: 0.6 μm) dispersion 42 parts by weight, carboxylic acid modified poly (vinyl alcohol) aqueous solution (manufactured by Gohsenol T-330, trade name, Nippon Synthetic Chemical Industry Co., Ltd .; solids content 10 %) 200 parts by weight, 100 parts by weight of an acrylic emulsion (SC-2250, trade name, Nippon Shokubai Co., Ltd .; solid content 40%), dimethylolurea solution (J-001, trade name, Showa Denko KK; solid content 30 %) 33 parts by weight, 40% zinc stearate dispersion (Highmicron F-930, trade name, Chukyo Yushi Co., Ltd .; average particle size 0.9 μm) 13 parts by weight, heavy calcium carbonate (NS- 1000, trade name, Nitto Funka Kogyo Co., Ltd.) 70 parts by weight, urethane acrylate emulsion (EM 90, trade name, Arakawa Chemical Industries Ltd .; solid content 40%) 25 parts by weight, polysiloxane (SM7025, trade name, Dow Corning Toray Silicone Co., Ltd .; coating for the intermediate layer by mixing 5 parts by weight of solid content and 33 parts by weight of water To prepare a fee.
    [1028] Example 120
    [1029] An example of the production of the two-color thermal recording material is described below.
    [1030] (A) Leuco dye for high temperature coloring layer: 3- (4'-dibutylamino-2'-hydroxyphenyl) -3- (5'-anilino-4'-methyl-2'-methoxyphenyl) phthalide .
    [1031] (B) Leuco dye for low temperature chromophoric layer: 3-diethylamino-7-chlorofluoran.
    [1032] (C) Color developer: Urea-urethane compound synthesized in Example 119.
    [1033] (D) sensitizer: diphenyl sulfone.
    [1034] 40 g of each organic compound of (A) to (D) is mixed with 40 g of 10% poly (vinyl alcohol) solution (polymerization degree 500, 90% saponification degree) and 20 g of water, and each of the obtained compositions is vertical In a sand mill (sand grinder manufactured by AIMEX CO., LTD.), Dispersion was carried out with a particle size of 1 μm, and each dispersion was prepared with liquids (A) to (D) corresponding to the above compounds (A) to (D). did.
    [1035] Meanwhile, 40 g of hard calcium carbonate (Brilliant 15, Shiraishi Industrial Co., Ltd .; average particle size 0.15 μm) and 60 g of 0.7% sodium hexametaphosphate solution were mixed, and the obtained composition was mixed in a Cowles disperser. Dispersed.
    [1036] Separately, 21% zinc stearate dispersion was prepared as lubricating dispersion (F), and 10% poly (vinyl alcohol) (NM11, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was prepared as adhesive liquid (G).
    [1037] Preparation of Coating Liquid (I) for High Temperature Coloring Thermal Layers
    [1038] The liquids (A), (C), (D) and (G) were blended so that the weight ratio after drying was as follows to prepare a coating liquid for a high temperature color-sensitive heat-sensitive layer:
    [1039] (A): (C): (E): (G) = 20: 40: 25: 15.
    [1040] Formation of High Temperature Coloring Thermal Layers
    [1041] High temperature color development by apply | coating said coating liquid for high temperature coloring heat-sensitive layer (I) in the quantity of 8 g / m <2> by dry weight using a Mayer bar on the quality paper (neutral paper) which has a reference weight of 60 g / m <2> . The heat-sensitive layer is formed.
    [1042] Preparation of Coating Liquid for Low Temperature Coloring Thermal Layer (II)
    [1043] The liquids (B), (C), (D), (E), (F) and (G) were blended so that the weight ratio after drying was as follows to prepare a coating liquid for a low temperature color heat-sensitive layer:
    [1044] (B): (C): (D): (E): (F): (G) = 10: 20: 20: 20: 10: 10.
    [1045] Preparation of Two-Color Thermal Recording Materials
    [1046] On the said high temperature coloring heat sensitive layer, said coating liquid for low temperature coloring heat-sensitive layer (II) was apply | coated by the dry weight in the quantity of 5 g / m <2> . Subsequently, Bekk smoothness (JIS-P8119) of the thermal recording surface was smoothed for 150 seconds using a supercalendar to obtain a two-color thermal recording material.
    [1047] Comparative Example 22
    [1048] A multicolored thermal recording material was produced and evaluated in the same manner as in Example 119, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound synthesized in Example 119. . The results obtained are summarized in Table 8.
    [1049] Comparative Example 23
    [1050] A two-color thermal recording material was prepared and evaluated in the same manner as in Example 120, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound used in Example 120. did. The results obtained are summarized in Table 8.
    [1051] Evaluation of Multicolored Thermal Recording Materials
    [1052] The multicolored thermal recording material obtained in Examples 119 and 120, and Comparative Examples 22 and 23 was printed using a commercially available thermal printer (NC-1, trade name, Fuji Photo Film Co., Ltd.), and image quality and image preservation It evaluated by the following method.
    [1053] [Quality]
    [1054] For five sheets of each recording material, the sharpness, contrast, density nonuniformity of the image, etc. were visually judged and evaluated in the following five grades: : Good, To : Somewhat good, : usually, -X: Somewhat defective, x: Poor.
    [1055] [Image Preservation]
    [1056] Each recording material was inserted between vinyl chloride wrap films or into vinyl chloride piles and a load of 300 g / cm 2 was applied from above. After standing at 40 ° C. for 24 hours, the color density of the print portion and the non-print portion (original recording material surface) were visually evaluated. When the print density is only slightly reduced, print preservation is evaluated to be good.
    [1057] The results obtained are shown in Table 8. In other words, the recording materials of Examples 119 and 120 have good image quality and exhibit excellent image retention, while the recording materials of Comparative Examples 22 and 23 are not as good as those of Examples 119 and 120.
    [1058]
    [1059] 1. Image quality
    [1060] Good.
    [1061] ~ Usually.
    [1062] × defective.
    [1063] 2. Plasticizer resistance (print preservation)
    [1064] ◎-It does not fade substantially.
    [1065] There is slight change in hue, but there is no scratch.
    [1066] Discoloration markedly.
    [1067] X ~ The color tone of printing disappears completely.
    [1068] Example 121
    [1069] A urea-urethane compound was synthesized in the same manner as in Example 24, and 2 g of the compound was pulverized and dispersed for 6 hours in a paint shaker with 8 g of a 2.5 wt% aqueous poly (vinyl alcohol) solution to prepare a dispersion. The temperature of the dispersion liquid immediately after the dispersion operation was 25 ° C. The diameter of the dispersed particles of the compound was 0.6 µm.
    [1070] 70 g of 3-dibutylamino-6-methyl-7-anilinofluorane together with 130 g of a 5.4 wt% poly (vinyl alcohol) aqueous solution was added at 2000 rpm in a sand grinder (manufactured by AIMEX CO., LTD .; tube volume 400 mL). Another dispersion was prepared by grinding and dispersing for 3 hours at rotational speed.
    [1071] Further, 70 g of diphenylsulfone was ground and dispersed in a sand grinder (manufactured by AIMEX CO., LTD .; pipe volume: 400 mL) with 130 g of a 5.4 wt% poly (vinyl alcohol) aqueous solution at a rotation speed of 2000 rpm for 3 hours. Another dispersion was prepared.
    [1072] In addition, 10 g of calcium carbonate and 30 g of water were mixed, and another dispersion was obtained by stirring the mixture using a stirrer.
    [1073] Meanwhile, a mixture of 60 parts by weight of aluminum hydroxide and 40 parts by weight of an aqueous solution of 12.5% by weight poly (vinyl alcohol) was treated with a sand grinder for 2 hours so that the aluminum hydroxide was brought to an average particle size of about 1 μm. It disperse | distributed and the aluminum hydroxide dispersion liquid was prepared.
    [1074] The dispersion and the other components were stirred and mixed in the following proportions (dry basis ratio) to obtain a coating solution: 20 parts by weight of a dry solid of the dispersion of the compound, 3-dibutylamino-6-methyl-7-anilinofluor 10 parts by weight of the dry solids of the column dispersion, 25 parts by weight of the dry solids of the diphenyl sulfone dispersion, 40 parts by weight of the dry solids of the calcium carbonate dispersion, 13 parts by weight of the dry solids of the aluminum hydroxide dispersion, and zinc stearate dispersion (solid Content of 20% by weight of dry solids of 16% by weight) and 15 parts by weight of dry solids of 15% by weight of poly (vinyl alcohol).
    [1075] Subsequently, the coating liquid for thermal recording layer was applied on an aluminum deposition paper at a rate of 50 m / min using a gravure coater (200 mesh; plate depth 20 mu). The treated aluminum vapor-deposited paper was dried at 80 ° C. for 3 seconds to obtain a heat-sensitive recording layer having a thickness of 2 μ. Next, a clear coating liquid composed of an aqueous dispersion of an acrylic resin (mainly composed of methyl methacrylate units, 2-ethylhexyl acrylate units and styrene units, having a glass transition temperature of about 40 ° C.) was coated on an aluminum deposition paper. It applied to the surface with the thickness of 8 micrometers using a roll coater, and it dried for 10 second at 80 degreeC, and obtained the metal deposition paper for laser markings which concerns on this invention.
    [1076] The laser beam from the carbon dioxide laser was irradiated to the metal deposition paper. A clear mark could be obtained and color development was good. A plasticizer resistance test was conducted by injecting the metal deposited paper between the wrap films to find that the plasticizer resistance was good enough that no fading of the printed portion was caused. The results obtained are summarized in Table 9.
    [1077] Example 122
    [1078] A urea-urethane compound was synthesized in the same manner as in Example 85, and 2 g of the compound was pulverized and dispersed in a paint shaker for 6 hours with 8 g of 2.5 wt% aqueous poly (vinyl alcohol) solution to prepare a dispersion.
    [1079] Subsequently, instead of the dispersion of the compound obtained in Example 121, a dispersion of the compound was used, and metal deposition for laser marking was performed in the same manner as in Example 121, except that diphenyl sulfone was used instead of aluminum hydroxide. Paper was prepared and evaluated. The results obtained are summarized in Table 9.
    [1080] Comparative Example 24
    [1081] A metal deposition paper for laser marking was prepared and evaluated in the same manner as in Example 121, except that 2,2-bis (4-hydroxyphenyl) propane was used instead of the urea-urethane compound synthesized in Example 121. . The results obtained are summarized in Table 9.
    [1082] [Color development sensitivity]
    [1083] An article for laser marking was irradiated with a laser beam with an energy of 0.6 J / cm 2 from a carbon dioxide laser (manufactured by Unimark, USHIO INC.) Through a stencil that can represent a number. If a clear mark is obtained and the color development concentration is high, the color development sensitivity is evaluated to be good.
    [1084] [Plasticizer resistance]
    [1085] Three vinyl chloride wrap films were placed on top and bottom of the marked laser marking article surface, and the obtained assembly was left at 40 ° C. for 24 hours under a load of 300 kg / cm 2 . After standing, the color density of the printed portion was visually evaluated. If the print density is only slightly reduced, print preservation is evaluated as good.
    [1086]
    [1087] 1. Marking sensitivity
    [1088] ◎-Good color development. Clear marks can be obtained.
    [1089] Although color development is somewhat inadequate, there is no problem in visibility.
    [1090] X ~ low color development, unclear printing.
    [1091] 2. Plasticizer resistance (print preservation)
    [1092] ◎-It does not fade substantially.
    [1093] There is slight change in hue, but there is no scratch.
    [1094] Discoloration markedly.
    [1095] X ~ The color tone of printing disappears completely.
    [1096] Example 123
    [1097] (1) Production of upper layer paper
    [1098] NISSEKI HISOL N-296 (oil, trade name, manufactured by Nippon Sekiyu Kagaku KK) was prepared by dissolving 2.5 parts by weight of 3-diethylamino-7-chlorofluorane in 80 parts by weight of a small amount of styrene-maleic anhydride copolymer. It was emulsified in 100 parts by weight of a 5% aqueous solution of pH 4.0 prepared by dissolving with sodium hydroxide of. Meanwhile, a mixture of 10 parts by weight of melamine, 25 parts by weight of 37% aqueous formaldehyde solution and 65 parts by weight of water was adjusted to pH 9.0 using sodium hydroxide and heated at 60 ° C., after 15 minutes the mixture was clear. Melamine formaldehyde precondensate was obtained. The initial condensate was added to the obtained emulsion and the mixture obtained was stirred for 4 hours while maintaining the mixture at 60 ° C., then cooled to room temperature. The solids content of the obtained microcapsule dispersion was 45%.
    [1099] The obtained microcapsule dispersion was applied onto paper and dried to obtain an upper layer paper.
    [1100] (2) manufacture of lower strata
    [1101] A dispersion was prepared by pulverizing and dispersing 15 g of the composition synthesized in the same manner as in Example 7, with 45 g of an aqueous 2% by weight poly (vinyl alcohol) solution in a paint shaker at room temperature for 45 minutes.
    [1102] Another dispersion was prepared by mixing 60 g of calcium carbonate and 90 g of water and mixing the mixture using a stirrer.
    [1103] A coating solution was prepared by mixing and stirring 40 parts by weight of the dispersion of the composition, 125 parts by weight of calcium carbonate dispersion and 120 parts by weight of an aqueous 10% by weight poly (vinyl alcohol) solution.
    [1104] The coating liquid was applied to a base paper having a reference weight of 40 g / m 2 using a bar coater of No. 10 to obtain a lower layer paper.
    [1105] The evaluation result of the said color development density | concentration was favorable with optical density 0.7.
    [1106] The evaluation result of solvent resistance using the hand cream was so good that the printing part could be read. The results obtained are summarized in Table 10.
    [1107] Comparative Example 25
    [1108] A pressure-sensitive recording material was produced and evaluated in the same manner as in Example 123 except that instead of using the active clay as the developer, instead of the urea-urethane compound used in Example 123. The results obtained are summarized in Table 10.
    [1109]
    [1110] 1. As the optical density (OD value) increases, the coloring density increases.
    [1111] 2. Solvent resistance (hand cream)
    [1112] ◎-It does not fade substantially.
    [1113] There is slight change in hue, but there is no scratch.
    [1114] Discoloration markedly.
    [1115] X ~ The color tone of printing disappears completely.
    [1116] By using a specific urea-urethane compound, it is possible to provide a coloring composition and a recording material excellent in image preservation and excellent in color development sensitivity at low cost.
    权利要求:
    Claims (89)
    [1" claim-type="Currently amended] A urea-urethane compound represented by the following formula (c) and having a molecular weight of 5000 or less:
    [Formula c]
    [Wherein R is an aliphatic compound residue,
    A 1 and A 2 are independently aromatic compound residues,
    The nitrogen atom of the urea group is directly bonded to the carbon atoms of the aromatic rings of A 1 and A 2 , respectively,
    R, A 1 and A 2 may have one or more substituents.
    [2" claim-type="Currently amended] Urea-urethane compound, characterized in that represented by the formula d:
    [Formula d]
    [Wherein R is an aliphatic compound residue,
    Hydrogen atoms of each benzene ring include aromatic compound residues, aliphatic compound residues, heterocyclic compound residues, hydroxyl groups, nitro groups, nitrile groups, carbamoyl groups, sulfamoyl groups, carboxyl groups, nitroso groups, amino groups, May be substituted with an oxyamino group, nitroamino group, hydrazino group, ureido group, isocyanate group, mercapto group, sulfo group or halogen atom,
    R may have one or more substituents.
    [3" claim-type="Currently amended] A urea-urethane compound represented by the following formula (e) or (f), having at least one urethane group and at least one urea group in total of 3 to 10 or less and a molecular weight of 5000 or less:
    [Formula e]
    [Wherein R is an aliphatic compound residue,
    Y is an aromatic compound residue, a heterocyclic compound residue, or an aliphatic compound residue,
    α 1 is an aromatic, heterocyclic or aliphatic compound residue different from Y and having two or more valences,
    n is an integer of 2 or more,
    Each residue may have one or more substituents; or
    [Formula f]
    [Wherein, Z 1 and Y are independently an aromatic compound residue or a heterocyclic compound residue,
    β 1 is an aliphatic compound residue having a valency of 2 or more,
    n is an integer of 2 or more,
    Each residue may have one or more substituents.
    [4" claim-type="Currently amended] Urea-urethane compound, characterized in that represented by the formula g or h:
    [Formula g]
    [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group. Can be substituted with an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom,
    β 1 is an aliphatic compound residue having a valency of 2 or more,
    n is an integer of 2 or more,
    Each residue may have one or more substituents; or
    [Formula h]
    [Wherein R is independently an aliphatic compound residue,
    The hydrogen atom of each benzene ring may be substituted with an aromatic compound residue, an aliphatic compound residue or a heterocyclic compound residue,
    Each residue may have one or more substituents,
    γ 1 is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C ( CF 3 ) 2- , -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2), and a group consisting of any group represented by the following formula a The group is selected from or does not exist:
    [Formula a] ].
    [5" claim-type="Currently amended] A urea-urethane composition comprising a urea-urethane compound and a diluent.
    [6" claim-type="Currently amended] 6. The urea-urethane composition according to claim 5, wherein the diluent is a urea compound and / or a urethane compound.
    [7" claim-type="Currently amended] 6. The urea-urethane composition according to claim 5, wherein the diluent is a compound obtained by reacting a polyisocyanate compound with a hydroxy compound or an amino compound.
    [8" claim-type="Currently amended] As a urea-urethane composition obtained by reacting a polyisocyanate compound with a hydroxy compound and an amino compound,
    A urea-urethane composition having at least one urea group and at least one urethane group in a molecular structure in total and containing at least 50% by weight of a urea-urethane compound having a molecular weight of 5000 or less.
    [9" claim-type="Currently amended] 9. The urea-urethane composition according to claim 8, wherein the hydroxy compound is a phenolic compound.
    [10" claim-type="Currently amended] 9. The urea-urethane composition according to claim 8, wherein the hydroxy compound is an alcohol compound.
    [11" claim-type="Currently amended] The urea-urethane composition according to any one of claims 8 to 10, wherein the amino compound is an aromatic amino compound.
    [12" claim-type="Currently amended] The urea-urethane composition according to any one of claims 8 to 11, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.
    [13" claim-type="Currently amended] The polyisocyanate compound and the hydroxy compound are reacted under a condition such that the ratio of the molar number of the polyisocyanate compound / hydroxyl equivalent number of the hydroxy compound is from 100/1 to 1/2 to obtain a portion of the isocyanate group of the polyisocyanate compound. And after forming at least one urethane group, an amino compound is added thereto to react the remaining isocyanate groups of the polyisocyanate compound with the amino compound to form at least one urea group.
    [14" claim-type="Currently amended] The polyisocyanate compound and the amino compound are reacted under conditions such that the ratio of the molar number of the polyisocyanate compound to the amino equivalent number of the amino compound is from 100/1 to 1/2, so that at least one urea is from a part of the isocyanate group of the polyisocyanate compound. After forming the group, a hydroxy compound is added thereto to react the remaining isocyanate group of the polyisocyanate compound with the hydroxy compound to form at least one urethane group.
    [15" claim-type="Currently amended] The process for producing a urea-urethane composition according to claim 13 or 14, wherein the reaction for forming at least one urethane group and the reaction for forming at least one urea group are carried out continuously.
    [16" claim-type="Currently amended] The polyisocyanate adduct obtained by the reaction of the polyisocyanate compound with the hydroxy compound is reacted such that the equivalent ratio of the amino compound and the isocyanate group / amino group is 2/1 to 1/100 to form one or more urea groups, A method for preparing a urea-urethane composition comprising removing an unreacted amino compound.
    [17" claim-type="Currently amended] The polyisocyanate adduct obtained by the reaction of the polyisocyanate compound with the amino compound is reacted such that the equivalent ratio of the hydroxy compound and the isocyanate group / hydroxyl group is 2/1 to 1/100 to form at least one urethane group. A process for producing a urea-urethane composition comprising removing an unreacted hydroxy compound.
    [18" claim-type="Currently amended] The method according to any one of claims 13 to 17,
    Reactions that form one or more urethane groups and / or reactions that form one or more urea groups without solvent, or
    A process for producing a urea-urethane composition, characterized in that the reaction of forming one or more urethane groups and / or the reaction of forming one or more urea groups is carried out using the same solvent.
    [19" claim-type="Currently amended] 19. The urea-urethane composition of any of claims 13 to 18, wherein the reaction to form at least one urethane group and / or the reaction to form at least one urea group is carried out at a temperature of 0 to 300 ° C. Manufacturing method.
    [20" claim-type="Currently amended] 20. The process according to any one of claims 13 to 19, wherein the reaction to form at least one urethane group and / or the reaction to form at least one urea group is carried out in the presence of a catalyst.
    [21" claim-type="Currently amended] A color developing composition containing a urea-urethane compound-containing developer.
    [22" claim-type="Currently amended] A color developing composition containing a urea-urethane compound-containing developer and a colorless or light-colored dye precursor.
    [23" claim-type="Currently amended] 23. The color-forming composition of claim 22, wherein the colorless or pale dye precursor is a leuco dye.
    [24" claim-type="Currently amended] The urea-urethane compound according to any one of claims 21 to 23, the urea according to any one of claims 5 to 12. -A color-forming composition, characterized in that it is a urethane composition or a composition produced by the production method according to any one of claims 13 to 20.
    [25" claim-type="Currently amended] 25. The leuco dye according to claim 23 or 24, wherein the leuco dye is at least one leuco dye selected from triarylmethane-based leuco dyes, fluorane-based leuco dyes, fluorene-based leuco dyes and diphenylmethane-based leuco dyes. Color development composition.
    [26" claim-type="Currently amended] The chromophoric composition according to claim 23 or 24, wherein the leuco dye is a compound represented by the following formula:
    [Formula ⅰ]
    [Wherein Y 2 and Y 3 are both an alkyl group or an alkoxyalkyl group,
    Y 4 is a hydrogen atom, an alkyl group or an alkoxy group,
    Y 5 and Y 6 are each a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group].
    [27" claim-type="Currently amended] The color-forming composition according to claim 23 or 24, wherein the leuco dye is a compound represented by the following formula:
    [Formula j]
    [Wherein R 5 and R 6 are each a group represented by the following formula k or formula l:
    [Formula k]
    Wherein each of R 11 to R 15 is a hydrogen atom, a halogen atom, a C 1 -C 8 alkyl group, a C 1 -C 8 alkoxy group, or each of R 16 and R 17 is an alkyl group having 1 to 8 carbon atoms -NR 16 R 17 }, or
    [Formula l]
    {Wherein, R 18 and R 19 are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a phenyl group};
    Each of R 7 to R 10 is a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or each of R 20 and R 21 is an alkyl group of 1 to 8 carbon atoms -NR 20 R 21 ].
    [28" claim-type="Currently amended] 28. The color developing composition according to any one of claims 21 to 27, wherein the melting point of the urea-urethane compound developer is 40 ° C or more and 500 ° C or less.
    [29" claim-type="Currently amended] 28. The color-forming composition according to any one of claims 21 to 27, wherein the urea-urethane compound developer contains a compound selected from compounds represented by the following formula (V) or (VI):
    [Formula Ⅴ]
    [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a nitro group, a hydroxyl group, a carboxyl group, a nitroso group, a nitrile group, a carbamoyl group, a ureido group. , Isocyanate group, mercapto group, sulfo group, sulfamoyl group or halogen atom, each moiety may have a substituent,
    γ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH- (wherein n is 1 or 2), and The group is selected from the group consisting of any of the groups shown, or does not exist:
    [Formula a] ]; And
    [Formula VI]
    [In formula, the hydrogen atom of each benzene ring is an aromatic compound residue, an aliphatic compound residue, a heterocyclic compound residue, a hydroxyl group, a nitro group, a nitrile group, a carbamoyl group, a sulfamoyl group, a carboxyl group, a nitroso group. May be substituted with an amino group, an oxyamino group, a nitroamino group, a hydrazino group, a ureido group, an isocyanate group, a mercapto group, a sulfo group or a halogen atom, and each residue may have one or more substituents,
    δ is -SO 2- , -O-,-(S) n -,-(CH 2 ) n- , -CO-, -CONH-, -NH-, -CH (COOR 1 )-, -C (CF 3 ) 2 -and -CR 2 R 3- (wherein R 1 , R 2 and R 3 are each an alkyl group and n is 1 or 2) or not present.
    [30" claim-type="Currently amended] 28. The color-forming composition according to any one of claims 21 to 27, wherein the urea-urethane compound developer contains a compound selected from compounds represented by the following formulas (XX) and (XXI).
    [Formula XX]
    [Formula XXI] .
    [31" claim-type="Currently amended] 31. A chromophoric composition according to any of claims 21 to 30, further comprising a heat-meltable material.
    [32" claim-type="Currently amended] 32. The method of claim 31, wherein the heat-fusible material is β-naphthylbenzyl ether, p-benzylbiphenyl, 1,2-di (m-methylphenoxy) ethane, di-p-methylbenzyl oxalate, 1,2 A chromogenic composition, characterized in that it is at least one compound selected from diphenoxymethylbenzene, m-terphenyl and stearamide.
    [33" claim-type="Currently amended] 32. The color-coating composition according to claim 31, wherein the thermally fusible material is represented by the following Chemical Formula X ':
    [Formula X ']
    [Wherein Y is -SO 2 -,-(S) n- , -O-, -CO-, -CH 2- , -CH (C 6 H 5 )-, -C (CH 3 ) 2- , -COCO-, -CO 3 -, -COCH 2 CO-, -COOCH 2 -, -CONH-, -OCH 2 - , and -NH- {wherein, n is 1 or 2} and either one of,
    The hydrogen atom of each benzene ring is a halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanate group, isothiocyanate group, mercapto group, sulfamoyl group, sulfonic acid group, amino group, aromatic compound residue , An aliphatic compound residue or a heterocyclic compound residue.
    [34" claim-type="Currently amended] The color-coating composition of claim 33, wherein the heat-meltable material is represented by the following Chemical Formula X ':
    [Formula X ']
    [Wherein, the hydrogen atom of each benzene ring is a halogen atom, hydroxyl group, nitro group, nitroso group, nitrile group, isocyanate group, isothiocyanate group, mercapto group, sulfamoyl group, sulfonic acid group, amino group , Aromatic compound residues, aliphatic compound residues or heterocyclic compound residues.
    [35" claim-type="Currently amended] 35. The color-forming composition according to any one of claims 21 to 34, which further contains an isocyanate compound.
    [36" claim-type="Currently amended] 35. The coloring composition according to any one of claims 21 to 34, further comprising an isocyanate compound and an imino compound.
    [37" claim-type="Currently amended] 37. A color developing composition according to any one of claims 21 to 36, further comprising an amino compound.
    [38" claim-type="Currently amended] 38. The color developing composition according to any one of claims 21 to 37, wherein the developer further contains an acidic developer.
    [39" claim-type="Currently amended] The method of claim 38, wherein the acidic developer is 2,2-bis (4-hydroxyphenyl) propane, 4-isopropyloxyphenyl-4'-hydroxyphenyl-sulfone, bis (3-allyl-4-hydroxy Color development, characterized in that it is at least one developer selected from oxyphenyl) sulfone, 2,4'-dihydroxydiphenylsulfone and 4,4 '-[oxybis (ethyleneoxy-p-phenylenesulfonyl)] diphenol Composition.
    [40" claim-type="Currently amended] 40. The color developing composition according to any one of claims 21 to 39, further comprising a fluorescent dye.
    [41" claim-type="Currently amended] 41. The color developing composition according to any one of claims 21 to 40, further comprising a shelf-stability imparting agent.
    [42" claim-type="Currently amended] A recording material comprising a support and a color developing layer formed on the support,
    The chromophoric layer is a urea-urethane compound according to any one of claims 1 to 4, a urea-urethane composition according to any one of claims 5 to 12, or a color-forming composition according to any one of claims 21 to 41. And a recording material comprising:
    [43" claim-type="Currently amended] 43. The recording material as claimed in claim 42, wherein a protective layer of a coloring layer is formed on the coloring layer.
    [44" claim-type="Currently amended] 44. The recording material of claim 43, wherein the protective layer contains a water-soluble polymer.
    [45" claim-type="Currently amended] 45. The recording material of claim 43 or 44, wherein the protective layer contains an inorganic pigment and / or an organic pigment.
    [46" claim-type="Currently amended] 46. The recording material as claimed in any one of claims 43 to 45, wherein the protective layer contains a lubricant.
    [47" claim-type="Currently amended] 43. The recording material as claimed in claim 42, wherein an intermediate layer is formed on the support, and a color developing layer is formed on the intermediate layer.
    [48" claim-type="Currently amended] 48. The recording material of claim 47, wherein the intermediate layer contains a water-soluble polymer.
    [49" claim-type="Currently amended] 49. The recording material of claim 47 or 48, wherein the intermediate layer contains an inorganic pigment and / or an organic pigment.
    [50" claim-type="Currently amended] 43. The recording material as claimed in claim 42, wherein a back coating layer is formed on the support on the side opposite to the surface on which the color developing layer is formed.
    [51" claim-type="Currently amended] 51. The recording material as claimed in claim 50, wherein the back coating layer contains a water soluble polymer.
    [52" claim-type="Currently amended] 52. The recording material as claimed in claim 50 or 51, wherein the back coat layer contains an inorganic pigment and / or an organic pigment.
    [53" claim-type="Currently amended] 53. The recording material according to any one of claims 42 to 52, wherein at least one compound selected from a water-soluble polymer and an anionic surfactant is used as a dispersant for the urea-urethane compound.
    [54" claim-type="Currently amended] The dispersant of the urea-urethane compound according to any one of claims 42 to 52, wherein the poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropyl-methyl cellulose, condensed sodium naphthalene sulfo A recording material using at least one compound selected from nitrate, polycarboxylic acid ammonium salt, water soluble low molecular weight copolymer, and sodium 2-ethylhexylsulfosuccinate.
    [55" claim-type="Currently amended] 55. The recording material according to any one of claims 42 to 54, wherein at least one compound selected from a water-soluble polymer, a nonionic surfactant and an anionic surfactant is used as a dispersant for the dye precursor.
    [56" claim-type="Currently amended] The dispersant of the dye precursor according to any one of claims 42 to 54, wherein methyl cellulose, hydroxypropylmethyl cellulose, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether sulfate and sodium 2-ethylhexylsulfosuccinate A recording material characterized by using at least one compound selected from nates.
    [57" claim-type="Currently amended] 57. The recording material according to any one of claims 42 to 56, wherein the recording material is a thermal recording material.
    [58" claim-type="Currently amended] 59. The thermal recording material of claim 57, wherein the average particle size of the urea-urethane compound is 0.05 µm or more and 5 µm or less.
    [59" claim-type="Currently amended] 59. The thermal recording material according to claim 57 or 58, wherein the liquid temperature at the time of grinding the urea-urethane compound is 60 ° C or less.
    [60" claim-type="Currently amended] 60. The thermal recording material according to any one of claims 57 to 59, wherein the pH at the time of grinding the urea-urethane compound is 5 to 10.
    [61" claim-type="Currently amended] 61. The thermosensitive recording material according to any one of claims 57 to 60, wherein at least one compound selected from a water-soluble polymer and an anionic surfactant is used as the dispersant for the heat-fusible material.
    [62" claim-type="Currently amended] 61. The method according to any of claims 57 to 60, wherein as the dispersant of the heat-fusible material, poly (vinyl alcohol), modified poly (vinyl alcohol), methyl cellulose, hydroxypropylmethyl cellulose, condensed sodium naphthalene sulfonate, A recording material using at least one compound selected from polycarboxylic acid ammonium salts, water soluble low molecular weight copolymers, and sodium 2-ethylhexylsulfosuccinate.
    [63" claim-type="Currently amended] 63. The thermosensitive recording material according to any one of claims 57 to 62, wherein the urea-urethane compound and the heat-fusible material are finely ground at the same time.
    [64" claim-type="Currently amended] 64. The thermal recording material according to any one of claims 57 to 63, wherein the pH of the support surface coated with the thermal recording layer of the thermal recording material is 3 to 9.
    [65" claim-type="Currently amended] 65. A method of manufacturing the thermal recording material according to any one of claims 57 to 64, wherein a thermal coating liquid having a pH of 5 to 12 is applied onto the support to form a thermal recording layer of the thermal recording material.
    [66" claim-type="Currently amended] 43. The recording material of claim 42, wherein the recording material is a thermal magnetic recording material.
    [67" claim-type="Currently amended] 67. A thermal magnetic recording material according to claim 66, wherein a thermal recording layer containing a urea-urethane compound developer is formed on one side of the support, and a magnetic recording layer is formed on the other side.
    [68" claim-type="Currently amended] 68. A train ticket which is a thermal magnetic recording material according to claim 66 or 67.
    [69" claim-type="Currently amended] A ticket ticket which is a thermal magnetic recording material according to claim 66 or 67.
    [70" claim-type="Currently amended] 43. The recording material of claim 42, wherein the recording material is a thermal recording label.
    [71" claim-type="Currently amended] The label for thermal recording according to claim 70, wherein a recording layer containing a urea-urethane compound developer is formed on one side of the support, and an adhesive layer is formed on the other side.
    [72" claim-type="Currently amended] 72. The label for thermal recording according to claim 71, wherein a back coating layer is formed between the adhesive layer and the support.
    [73" claim-type="Currently amended] 72. The label for thermal recording according to claim 71 or 72, wherein an intermediate layer is formed between the thermal recording layer and the support.
    [74" claim-type="Currently amended] 74. The label for thermal recording according to any one of claims 71 to 73, wherein a protective layer is formed on the thermal recording layer.
    [75" claim-type="Currently amended] 43. The recording material of claim 42, wherein the recording material is a multicolor thermal recording material.
    [76" claim-type="Currently amended] 76. The multicolor thermal recording material having at least two thermal recording layers formed on one side of a support, wherein the recording material contains a urea-urethane compound developer in at least one of the thermal recording layers. Thermal recording material.
    [77" claim-type="Currently amended] 77. The multicolored thermosensitive recording material of claim 76, wherein an intermediate layer is formed between the thermosensitive recording layers.
    [78" claim-type="Currently amended] A multicolored thermosensitive recording material comprising a support and two thermal recording layers laminated on one side of the support,
    One side of the support is formed by laminating a thermal recording layer having a different color development temperature and developing a different color tone, respectively, and the upper thermal recording layer is an agent used as both a color developer and a color developer, or a reversible developer. And a urea-urethane compound developer in the lower thermal recording layer.
    [79" claim-type="Currently amended] 79. The method of claim 78, wherein, among the two heat-sensitive recording layers, an upper layer is a low temperature chromophoric layer that can develop at low temperature, and can be discolored at high temperature, and a lower layer is a high temperature chromogenic layer that can develop at high temperature. Multi-color thermal recording material.
    [80" claim-type="Currently amended] An article for laser marking, characterized by having a thermally sensitive recording layer containing a urea-urethane compound developer on its surface.
    [81" claim-type="Currently amended] An article for laser marking, comprising a thermally sensitive recording layer containing a colorless or pale dye dye precursor, a urea-urethane compound developer, and a recording sensitivity improving agent.
    [82" claim-type="Currently amended] 84. The article for laser marking according to claim 80 or 81, having a protective layer containing an aqueous binder having a glass transition temperature of 20 to 80 deg. C on the thermal recording layer.
    [83" claim-type="Currently amended] 84. The article of claim 81, wherein the recording sensitivity enhancer is one or more compounds selected from aluminum hydroxide, muscovite, wollastonite, and kaolin.
    [84" claim-type="Currently amended] 84. The article according to any one of claims 80 to 83, wherein the article is any one of labels, packaging materials and containers.
    [85" claim-type="Currently amended] A method for producing an article for laser marking, comprising applying a color marking composition containing a urea-urethane compound developer onto a support, and drying the treated support as described above.
    [86" claim-type="Currently amended] A method for producing an article for laser marking, comprising applying a color marking composition containing a colorless or pale dye precursor, a urea-urethane compound developer and a recording sensitivity enhancer on a support, and drying the treated support as described above. .
    [87" claim-type="Currently amended] 84. A marking method for an article, characterized by irradiating laser light to the thermal recording layer of the article for laser marking according to any one of claims 80 to 84.
    [88" claim-type="Currently amended] A color marking composition comprising a urea-urethane compound developer.
    [89" claim-type="Currently amended] A color marking composition comprising a colorless or pale dye precursor, a urea-urethane compound developer and a recording sensitivity enhancer.
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    同族专利:
    公开号 | 公开日
    CN1303064C|2007-03-07|
    CA2399054A1|2001-09-13|
    CN1496346A|2004-05-12|
    AU779924B2|2005-02-17|
    WO2001066515A1|2001-09-13|
    KR100549037B1|2006-02-02|
    AU3602901A|2001-09-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-03-02|Priority to JP2000057693
    2000-03-02|Priority to JPJP-P-2000-00057693
    2000-03-02|Priority to JP2000057538
    2000-03-02|Priority to JPJP-P-2000-00057538
    2000-03-03|Priority to JPJP-P-2000-00058468
    2000-03-03|Priority to JPJP-P-2000-00059298
    2000-03-03|Priority to JP2000058823A
    2000-03-03|Priority to JP2000059047
    2000-03-03|Priority to JPJP-P-2000-00058594
    2000-03-03|Priority to JP2000058279A
    2000-03-03|Priority to JPJP-P-2000-00058249
    2000-03-03|Priority to JP2000058249
    2000-03-03|Priority to JP2000059216A
    2000-03-03|Priority to JP2000059298
    2000-03-03|Priority to JPJP-P-2000-00058891
    2000-03-03|Priority to JP2000058891A
    2000-03-03|Priority to JPJP-P-2000-00059047
    2000-03-03|Priority to JP2000058861A
    2000-03-03|Priority to JPJP-P-2000-00058770
    2000-03-03|Priority to JPJP-P-2000-00059216
    2000-03-03|Priority to JP2000058594A
    2000-03-03|Priority to JPJP-P-2000-00058861
    2000-03-03|Priority to JPJP-P-2000-00058823
    2000-03-03|Priority to JPJP-P-2000-00058279
    2000-03-03|Priority to JP2000058468A
    2000-03-03|Priority to JP2000058770A
    2000-09-04|Priority to JP2000267302
    2000-09-04|Priority to JPJP-P-2000-00267302
    2000-09-04|Priority to JP2000267467A
    2000-09-04|Priority to JPJP-P-2000-00267467
    2001-03-01|Application filed by 아사히 가세이 가부시키가이샤
    2001-03-01|Priority to PCT/JP2001/001577
    2003-01-23|Publication of KR20030007444A
    2006-02-02|Application granted
    2006-02-02|Publication of KR100549037B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000057538|2000-03-02|
    JPJP-P-2000-00057538|2000-03-02|
    JP2000057693|2000-03-02|
    JPJP-P-2000-00057693|2000-03-02|
    JP2000058823A|JP2001246858A|2000-03-03|2000-03-03|Heat-sensitive magnetic recording material|
    JP2000059047|2000-03-03|
    JPJP-P-2000-00058594|2000-03-03|
    JP2000058279A|JP2001246854A|2000-03-03|2000-03-03|Recording material|
    JPJP-P-2000-00058249|2000-03-03|
    JP2000058249|2000-03-03|
    JP2000059216A|JP2001246849A|2000-03-03|2000-03-03|New color former and heat sensitive recording material|
    JP2000059298|2000-03-03|
    JPJP-P-2000-00058891|2000-03-03|
    JP2000058891A|JP2001246860A|2000-03-03|2000-03-03|Coloring marking agent, marking method and marking article|
    JPJP-P-2000-00059047|2000-03-03|
    JP2000058861A|JP2001246859A|2000-03-03|2000-03-03|Heat-sensitive recording label|
    JPJP-P-2000-00058770|2000-03-03|
    JPJP-P-2000-00059216|2000-03-03|
    JP2000058594A|JP2001246856A|2000-03-03|2000-03-03|Heat-sensitive recording sheet|
    JPJP-P-2000-00058861|2000-03-03|
    JPJP-P-2000-00058823|2000-03-03|
    JPJP-P-2000-00058279|2000-03-03|
    JP2000058468A|JP2001246855A|2000-03-03|2000-03-03|Recording sheet|
    JP2000058770A|JP2001246857A|2000-03-03|2000-03-03|Multicolor heat-sensitive recording material|
    JPJP-P-2000-00058468|2000-03-03|
    JPJP-P-2000-00059298|2000-03-03|
    JP2000267467A|JP4577965B2|2000-03-03|2000-09-04|Thermal recording material and method for producing the same|
    JPJP-P-2000-00267467|2000-09-04|
    JP2000267302|2000-09-04|
    JPJP-P-2000-00267302|2000-09-04|
    PCT/JP2001/001577|WO2001066515A1|2000-03-02|2001-03-01|Novel color former and recording material|
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