• 专利附录
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    • 专利摘要:
    An object of the present invention is to provide a material having spectral characteristics, light resistance, solubility and thermal decomposition characteristics suitable for recording for DVD-R. More specifically, the present invention provides a metal complex squariarium compound of formula (I): Where R 1 and R 2 are the same or different and represent an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent, an aryl group optionally having a substituent or a heterocyclic group optionally having a substituent; Q represents a metal atom having coordination ability; q represents 2 or 3; A represents an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent, or Y = CH-, wherein Y represents an aryl group optionally having a substituent or a heterocyclic group optionally having a substituent.
    公开号:KR20020097177A
    申请号:KR1020027010528
    申请日:2001-12-19
    公开日:2002-12-31
    发明作者:시미즈이쿠오；도요다히로시；기누가사모토하루；야마다시호；노구치소；사토츠토무；도무라타츠야
    申请人:교와 핫꼬 고교 가부시끼가이샤；교와 유까 가부시키가이샤；
    IPC主号:
    专利说明:

    Metal complex type squarylium compounds and optical recording media made by using the same}
    [2] Recently, as a recordable optical recording medium having a higher recording density than CD-R (compact disc-recordable, compact disc), DVD-R (Digital Versatile Disc-Recordable, recordable digital versatile disc) Development is in progress. Both CD-R and DVD-R are similar in terms of using organic dyes as recording materials, and are similar in principle in recording and reproducing signals (information). Therefore, with respect to various properties (light resistance, solubility, and thermal decomposability) other than the spectral characteristics required for recording materials, organic dyes developed for CD-R can basically satisfy the requirements for DVD-R recording materials. Can be. However, the oscillation wavelength of the semiconductor laser used to record signals to or reproduce signals from the DVD-R is 600 to 700 nm, and this wavelength is shorter than the oscillation wavelength of the semiconductor laser used for CD-R. Therefore, when the recording material used in the DVD-R exists in the form of a film, it must have an absorption edge of a shorter wavelength range than the recording material of the CD-R. Therefore, dyes developed as recording materials for CD-Rs, such as cyanine dyes, azaannulene dyes and indoaniline-metal chelate dyes ("Electronics Related Dyes", CMC, 1998), are described as DVD- It cannot be used as a recording material for R.
    [3] The present inventors have conventionally developed a squariarium compound having two different kinds of aromatic substituents in the same molecule. Such a squariarium compound has a squaric acid skeleton at the center of the molecule, and has a structure having a substituent composed of an aromatic compound at two carbon atoms positioned on its diagonal. When these two aromatic substituents are identical, they are called symmetric squariarium compounds (or symmetric squariarium dyes) for convenience, and in other cases asymmetric squariarium compounds (or asymmetric squariarium dyes).
    [4] As a known squariarium compound which coordinates with a metal to form a chelate structure, there is a symmetric squariarium compound having an aniline derivative of the formula (A) as an aromatic substituent (Chem. Ber. Vol. 103, 3553-3562, 1970):
    [5]
    [6] However, this compound is not a structure in which a plurality of squariarium compounds are coordinated with one metal atom, but the nitrogen atom between the aromatic and squaric acid skeleton is involved in the coordination.
    [7] In addition, as a known compound in which a plurality of squariarium-like compounds are coordinated with metal atoms to form a chelate structure, there is a compound represented by the following formula (B) ("OXOCARBONS", ACADEMIC PRESS 1980, 210, by Robert West).
    [8] However, this compound is obtained by substituting a substituent on the squaric acid skeleton from an oxygen atom to a sulfur atom, where the nitrogen atom between the aromatic ring and the squaric acid skeleton is involved in coordination.
    [9]
    [10] Moreover, the complex of the compound of following formula (C) and a metal is known as an example which has the atom which is involved in coordination as a substituent of an aromatic ring, and the several squariarium compound formed the complex with one metal atom. This complex can be used, for example, as a near infrared absorber, a filter for a plasma display, or the like (Japanese Patent Laid-Open No. 2000-159776):
    [11]
    [12] Where
    [13] X and X 'represent a group having active hydrogen, Y 1 and Y 2 represent a hydrogen atom, an alkylamino group and the like, and k and k' represent an integer of 1 to 4.
    [14] However, in this publication, only the squariarium compound of following formula (D) is specifically disclosed as a squariarium compound corresponding to Formula (C), and neither a complex structure is disclosed specifically.
    [15]
    [16] Where
    [17] Z 1 to Z 6 represent a hydrogen atom, an alkyl group or the like.
    [18] Squariarium compounds having a structure in which a plurality of squariarium compounds are coordinated to one metal atom, and a structure in which the atoms involved in the coordination are oxygen atoms which are substituents on the squaric acid skeleton and atoms in one aromatic ring substituent are not known yet. not.
    [19] The spectral characteristics of the recording material, which are closely related to the recording sensitivity and reproduction sensitivity of the signal, have a maximum absorption wavelength (λ max ) of the recording material measured in solution, considering the oscillation wavelength of the semiconductor laser used in the DVD-R. It is preferable that it is in the range of ˜600 nm, and logε (ε is the molar extinction coefficient) at the maximum absorption wavelength is preferably 5 or more.
    [20] In addition, it is preferable that the thermal decomposition characteristics of the recording material closely related to the recording sensitivity be decomposed in the temperature range of 250 to 350 캜.
    [21] In addition to the properties of the recording material, light resistance and solubility in a solvent necessary for film formation are also required. When a known squariarium compound is used for the recording material for DVD-R, the recording material for DVD-R obtained has a spectral characteristic, It is not practically satisfactory in view of light resistance, solubility and thermal decomposition characteristics. Melting | fusing point of the compound (A) mentioned above is 350 degreeC or more, and the maximum absorption wavelength of a compound (C) is 830 nm, but there is no data regarding the characteristic of a compound (B).
    [1] The present invention relates to a squariarium compound usable in the field of optical recording and an optical recording medium using the same.
    [22] Disclosure of the Invention
    [23] An object of the present invention is to provide a squariarium compound having spectral characteristics, light resistance, solubility and thermal decomposition characteristics suitable for a recording material for DVD-R, and an optical recording medium using the same.
    [24] The present inventors have conducted studies in view of the above circumstances and found that a squaryrium compound having hydroxypyrazole as an aromatic substituent and a metal atom having a coordinating ability form a chelate complex. In addition, the finding that the compound obtained by forming such a chelate complex has desirable characteristics as a recording material for DVD-R.
    [25] SUMMARY OF THE INVENTION The present invention has been made on the basis of these findings to provide an optical recording medium having a squariarium compound of formula (I) and a recording layer containing the squariarium compound:
    [26]
    [27] Where
    [28] R 1 and R 2 are the same or different and represent an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent, an aryl group optionally having a substituent, or a heterocyclic group optionally having a substituent;
    [29] Q represents a metal atom having coordination ability;
    [30] q represents 2 or 3;
    [31] A represents an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent, or Y = CH-, wherein Y represents an aryl group optionally having a substituent or a heterocyclic group optionally having a substituent.
    [32] Hereinafter, the present invention will be described, in which the compound of formula (I) is referred to as compound (I). The same applies to compounds having other chemical formula numbers.
    [33] First, in the definition of each group for the general formula (I) or the general formula (II) described later, as the alkyl moiety in the alkyl group and the alkoxy group, for example, a linear or branched alkyl group having 1 to 6 carbon atoms and 3 And cyclic alkyl groups having from 8 to 8 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and isopen A methyl group, 1-methylbutyl group, 2-methylbutyl group, tert-pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc. are mentioned. .
    [34] As an aralkyl group, the aralkyl group which has 7-15 carbon atoms is mentioned, for example, A benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, etc. are mentioned as a specific example.
    [35] As an aryl group, a phenyl group, a naphthyl group, anthryl group, an azulenyl group etc. are mentioned, for example.
    [36] Examples of the halogen atom include chlorine atom, bromine atom, fluorine atom and iodine atom.
    [37] As the substituent of the aralkyl group, the aryl group, the alkoxy group, the aromatic ring, the heterocyclic ring or the heterocyclic group, the same or different 1 to 5 substituents, for example, hydroxyl group, carboxyl group, halogen atom, optionally substituent And an alkyl group having an alkyl group, an alkoxy group, a nitro group, an amino group optionally having a substituent, and the like. Examples of the halogen atom, alkyl group and alkoxy group include those mentioned above.
    [38] As a substituent of an alkyl group, the same or different 1-3 substituents, for example, a hydroxyl group, a carboxy group, a halogen atom, an alkoxy group, etc. are mentioned. Examples of the halogen atom and the alkoxy group include those mentioned above. Moreover, as a substituent of an alkyl group, the same thing as the substituent of the alkyl group mentioned later is mentioned.
    [39] Examples of the substituent for the amino group include the same or different one or two alkyl groups, and examples of the alkyl group in this case include those mentioned above.
    [40] Examples of the metal atom having coordination ability include aluminum, zinc, copper, iron, nickel, chromium, cobalt, manganese, iridium, vanadium, titanium, and the like. Among them, trivalent metals [eg, aluminum, Iron (III), chromium (III), cobalt (III), manganese (III), iridium (III), vanadium (III), etc.] are preferred, and aluminum is more preferred.
    [41] As an aromatic ring which two R <6> adjacent to each other form with two adjacent carbon atoms, a benzene ring, a naphthalene ring, an anthracene ring, etc. are mentioned.
    [42] The heterocycle in the heterocyclic group, or the heterocycle formed by R 3 and R 4 together with the adjacent carbon atom, includes, for example, 5- or at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom. 6-membered monocyclic aromatic or aliphatic heterocycle, fused di- or tri-cyclic formed by the fusion of 3- to 8-membered rings and comprising at least one atom selected from nitrogen, oxygen and sulfur atoms Aromatic or aliphatic heterocycle, and the like, and more specifically, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyri Dean ring, cinnaline ring, pyrrole ring, parasol ring, imidazole ring, triazole ring, tetrazole ring, thiophene ring, furan ring, thiazole ring, oxazole ring, indole ring, isoindole ring, indazole ring, Zimidazole ring, benzotriazole ring, benzothiazole ring, benzoxazole ring, purine ring, carbazole ring, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, arc A fur perazine ring, the tetrahydropyridine ring, the tetrahydroquinoline ring, the tetrahydroisoquinoline ring, the tetrahydrofuran ring, the tetrahydropyran ring, the dihydrobenzofuran ring, the tetrahydrocarbazole ring, an indoline ring, etc. are mentioned.
    [43] Examples of the alicyclic hydrocarbon ring formed by R 3 and R 4 together with adjacent carbon atoms include a saturated or unsaturated alicyclic hydrocarbon ring having 3 to 8 carbon atoms, and examples thereof include cyclopropane ring and cyclobutane ring. And cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclopentene ring, 1,3-cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring and the like.
    [44] In compound (I), compounds in which Y is an indolin ring optionally having a substituent are preferable, and among these, compounds in which Y = CH- is of the general formula (II) are more preferable:
    [45]
    [46] Where
    [47] R 3 and R 4 are the same or different and optionally represent an alkyl group having a substituent, or R 3 and R 4 together with the adjacent carbon atoms may form a cycloaliphatic hydrocarbon ring or a heterocycle having an optionally substituent;
    [48] R 5 represents a hydrogen atom, an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent or an aryl group optionally having a substituent;
    [49] R 6 represents a halogen atom, an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent, an aryl group optionally having a substituent, a nitro group, a cyano group or an alkoxy group optionally having a substituent;
    [50] n represents an integer of 0 to 4;
    [51] Herein, when n is 2 to 4, R 6 may be the same or different, and two adjacent R 6 may form an aromatic ring optionally having a substituent together with two adjacent carbon atoms.
    [52] Hereinafter, the general manufacturing method of compound (I) is demonstrated.
    [53] Scheme (1-a)
    [54]
    [55] Scheme (1-b)
    [56]
    [57] Scheme (1-c)
    [58]
    [59] Scheme (1-d)
    [60]
    [61] Where
    [62] R 1 , R 2 , A, Q and q are as defined above,
    [63] Y represents a hydrogen atom, potassium, sodium, or the like.
    [64] Scheme (1-a)
    [65] Compound (V) is obtained by reacting compound (III) with 0.7 to 1.5-fold molar amount of compound (IV), if necessary, at 0 to 80 ° C. for 5 minutes to 15 hours in a solvent in the presence of a base.
    [66] Examples of the base to be used include inorganic bases such as potassium carbonate, sodium carbonate and potassium hydroxide, and organic bases such as triethylamine and sodium methoxide. The preferred amount of base is 0.7 to 1.5 times molar relative to compound (III).
    [67] Examples of the solvent include methanol, ethanol, dimethylformamide and the like.
    [68] Scheme (1-b)
    [69] Compound (VI) is obtained by reacting compound (V) in an alkaline solvent or an acidic solvent at 0 to 80 ° C for 30 minutes to 15 hours.
    [70] Examples of the alkaline solvent used include aqueous potassium carbonate solution, aqueous sodium carbonate solution, aqueous potassium hydroxide solution and the like.
    [71] Examples of acidic solvents used include an aqueous solution of dimethylsulfoxide in 50 vol / vol% of hydrochloric acid, an aqueous solution of dimethylformamide in 50 vol / vol% of hydrochloric acid and the like.
    [72] Scheme (1-c)
    [73] Compound (VII) is obtained by reacting compound (VI) with 0.5 to 2 times molar A-H, if necessary, at 5 to 120 ° C. for 5 minutes to 15 hours in a solvent in the presence of 0.5 to 2 times molar base.
    [74] Examples of the solvent used include alcohol solvents alone having 2 to 8 carbon atoms such as ethanol, propanol, isopropyl alcohol, butanol, octanol, or a mixed solvent of these alcohol solvents with benzene, toluene or xylene (alcohol type). Preferably at least 50% by volume of solvent).
    [75] Examples of the base used include organic bases such as quinoline, triethylamine, pyridine and inorganic bases such as potassium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
    [76] Scheme (1-d)
    [77] Compound (I) is obtained by reacting compound (i) with a raw material for providing Q q + if necessary for 5 minutes to 15 hours at room temperature to 120 ° C. in a solvent in the presence of 0.5 to 2 times molar acetic acid. Raw material for providing Q q + is selected from the compounds (Ⅶ) number of moles of (number of moles of the raw material to provide the Q + q) of the q × ratio of 1: is preferably used so that 0.5 to 2.
    [78] Examples of raw materials for providing Q q + used include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum isopropoxide, aluminum sec-butoxide, aluminum ethoxide, aluminum chloride, copper chloride, acetic acid Copper, nickel acetate, and the like.
    [79] Examples of the solvent used include halogen solvents such as chloroform and dichloromethane; Aromatic solvents such as toluene and xylene; Ether solvents such as tetrahydrofuran and methyl-tert-butyl ether; Ester solvents such as ethyl acetate and the like.
    [80] Specific examples of the compound (I) are shown in Table 1. In addition, a compound number in a table corresponds to the Example number mentioned later. In the table, "Ph" represents a phenyl group, "Me" represents a methyl group, "Pr" represents a propyl group, and " i Pr" represents an isopropyl group.
    [81] Table 1 Specific Examples of Compounds
    [82]
    [83] Table 1 (Continued) Specific Examples of Compounds
    [84]
    [85] Table 1 (Continued) Specific Examples of Compounds
    [86]
    [87] Table 1 (Continued) Specific Examples of Compounds
    [88]
    [89] Table 1 (Continued) Specific Examples of Compounds
    [90]
    [91] Table 1 (Continued) Specific Examples of Compounds
    [92]
    [93] Next, the structure of the optical recording medium using the squariarium compound of the present invention (hereinafter also referred to as "compound of the present invention") is described.
    [94] Physical properties required for the recording layer materials include optical properties, thermal properties and light resistance.
    [95] As an optical characteristic, it preferably has a wider absorption band on the short wavelength side than 600 to 700 nm, more preferably 630 to 690 nm, which is a recording / reproducing wavelength such as DVD-R, and the recording / reproducing wavelength is near the long wavelength end of the absorption band. It is preferable. This means that the recording layer material has a large refractive index and a predetermined extinction coefficient at a recording reproduction wavelength of 600 to 700 nm.
    [96] Specifically, for the light in the wavelength region of the recording / reproducing wavelength of ± 5 nm near the long wavelength terminal of the absorption band, the refractive index n of the single layer of the recording layer is in the range of 1.5 to 3.0, and the extinction coefficient k is 0.02 to It is preferable to exist in the range of 3.0. If n is 1.5 or more, the reflectance and recording modulation degree are further increased. If n is 3.0 or less, a reproduction error does not occur in the light of the recording / reproducing wavelength region. In addition, when k is 0.02 or more, the recording sensitivity is better, and when k is 0.3 or less, a reflectance of 50% or more can be easily obtained.
    [97] In addition, it is preferable that the maximum absorption wavelength (λ max ) of the recording layer material measured in the chloroform solution state is in the range of 550 to 600 nm, and the larger the absorption coefficient, the larger the refractive index n, and therefore the logε at the maximum absorption wavelength. (ε molar extinction coefficient) is preferably 5 or more.
    [98] And as a thermal characteristic, it is preferable that a decomposition temperature exists in a specific temperature range. Specifically, the decomposition temperature is preferably 350 ° C. or lower, and more preferably in the range of 250 to 350 ° C. If the decomposition temperature is 350 ° C. or lower, the power of the recording laser beam does not need to be hardened. If the decomposition temperature is 250 ° C. or higher, the recording stability is preferable.
    [99] In terms of light resistance, it is desirable to have reproducibility stability of 1 million times or more and fastness that does not fade under room standing.
    [100] Preferable conditions for the shape of the substrate are those in which the track pitch on the substrate is in the range of 0.7 to 0.8 mu m, and the groove width is in the range of 0.18 to 0.40 mu m in half band width.
    [101] The substrate is preferably a substrate having a guiding groove having a depth of 1,000 to 2,500 mm 3. The track pitch is preferably 0.7 to 1.0 mu m, and more preferably 0.7 to 0.8 mu m for high density recording applications. The groove width is preferably half band width of 0.18 to 0.40 mu m. When the groove width is 0.18 mu m or more, sufficient strength of the tracking error signal can be easily obtained, and when the groove width is 0.40 mu m or less, the recording portion is rarely widened laterally during recording.
    [102] 1. Structure of optical record carrier
    [103] The optical recording medium of the present invention may be formed in an air-sandwich structure applied to a conventional write-once optical disc or in a close contact structure, or may be formed of a write-once optical recording medium such as a DVD-R or the like. Can be.
    [104] 2. Examples of necessary properties and components of each layer
    [105] The optical recording medium of the present invention has a structure in which the first substrate and the second substrate are bonded with an adhesive through the recording layer. The recording layer may be a single layer of the organic dye layer containing the compound of the present invention, or may be a laminated layer of the organic dye layer and the metal reflection layer to increase the reflectance. An undercoat layer or a protective layer may be formed between the recording layer and the substrate, or they may be laminated in order to improve the function. Preferable structural forms include a first substrate / organic dye layer / metal reflective layer / protective layer / adhesive layer / second substrate structure.
    [106] a. Board
    [107] The substrate to be used must have transparency to the wavelength of the laser beam to be used when recording or reproducing from the substrate side, but it is not necessary to have transparency to recording or reproducing from the recording layer side. As the material of the substrate, for example, a plastic, glass, ceramic or metal such as polyester, acrylic resin, polyamide, polycarbonate resin, polyolefin resin, phenol resin, epoxy resin, polyimide, or the like can be used. In addition, a tracking guide groove or guiding pit, a preformat such as an addressing signal, or the like may be formed on the substrate surface.
    [108] b. Recording layer
    [109] The recording layer is a layer in which any optical change occurs by irradiation of a laser beam and information is recorded by the change, and the recording layer should contain the compound of the present invention. In forming the recording layer, one of the compounds of the present invention may be used alone or in combination of two or more thereof.
    [110] In addition, the compound of the present invention may be mixed or laminated with other organic dyes, metals or metal compounds for the purpose of improving optical characteristics, recording sensitivity, signal characteristics and the like. Examples of the organic dyes include polymethine dyes, naphthalocyanine series, phthalocyanine series, squariarium series, croconium series, pyririum series, naphthoquinone series, anthraquinone series (indanthrene series), xanthene series, and triphenylmethane series. , Azulene-based, tetrahydrocholine-based, phenanthrene-based, triphenothiazine-based dyes, and metal complex compounds. Examples of metals and metal compounds include In, Te, Bi, Se, Sb, Ge, Sn, Al, Be, TeO 2 , SnO, As, Cd, etc., each of which may be used in the form of dispersion mixing or lamination. have.
    [111] In addition, it is possible to remarkably improve light resistance by mixing a light stabilizer with the compound of the present invention. As the light stabilizer, metal complexes and aromatic amines are preferable. Examples of specific light stabilizers are described later (see Tables 2 and 3).
    [112] The mixing ratio of the light stabilizer to the compound of the present invention is preferably 5 to 40% by weight. When the content is 5% by weight or more, the light stabilizing effect is high.
    [113] In addition, it is also possible to disperse and mix high molecular materials such as ionomer resins, polyamide resins, vinyl resins, natural polymers, silicones, liquid rubbers, silane coupling agents and the like in the compounds of the present invention. In order to improve properties, additives such as stabilizers (eg, transition metal complexes), dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers, and the like may be used together.
    [114] Formation of the recording layer can be carried out using conventional methods such as deposition, sputtering, chemical vapor deposition (CVD) or solvent coating. In the case of using the coating method, the dye to which the above-mentioned additives are added to the compound of the present invention as needed is dissolved in an organic solvent, and the solution is coated with a conventional coating such as spray, roller coating, dipping or spin coating. Can be done according to the law.
    [115] Examples of the organic solvent that can be used generally include alcohols such as methanol, ethanol and isopropyl alcohol; Ketones such as acetone, methyl ethyl ketone and cyclohexane; Amides such as N, N-dimethylformamide and N, N-dimethylacetoamide; Sulfoxides such as dimethyl sulfoxide; Ethers such as tetrahydrofuran, dioxane, diethyl ether and ethylene glycol monomethyl ether; Esters such as methyl acetate and ethyl acetate; Aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, carbon tetrachloride and trichloroethane; Aromatics such as benzene, xylene, monochlorobenzene and dichlorobenzene; Cellosolves such as methoxy ethanol and ethoxy ethanol; Hydrocarbons, such as hexane, a pentane, cyclohexane, and methyl cyclohexane, etc. are mentioned.
    [116] The film thickness of the recording layer is preferably 100 GPa to 10 µm, preferably 200 GPa to 2,000 GPa.
    [117] Below, the specific example of the light stabilizer which can be used together with the compound of this invention is shown.
    [118] 1) Metal Stabilizer Light Stabilizer (see Table 2)
    [119] (A)
    [120]
    [121] Where
    [122] R a and R b are the same or different and represent a hydrogen atom, an optionally substituted alkyl group, an aryl group or a heterocyclic group.
    [123] (B)
    [124]
    [125] Where
    [126] R a , R b , R c and R d are the same or different and represent an alkyl group, an aryl group, a cyclic alkyl group or a heterocyclic group which is bonded to a hydrogen atom, a halogen atom, directly or indirectly through a divalent linking group.
    [127] (C)
    [128]
    [129] Where
    [130] X represents O, S or CR a R b ,
    [131] Wherein R a and R b are the same or different and represent a group of atoms necessary to form CN, COR c , COOR d , CONR e R f , SO 2 R g , or a 5- or 6-membered ring,
    [132] R c to R g are the same or different and optionally represent an alkyl group or an aryl group having a substituent.
    [133] (D)
    [134]
    [135] Where
    [136] R a , R b , R c and R d are the same or different and represent an alkyl group, an aryl group, a cyclic alkyl group or a heterocyclic group which is bonded to a hydrogen atom, a halogen atom, directly or indirectly through a divalent linking group,
    [137] R e represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carboxy group, an alkoxycarbonylalkyl group or a sulfo group.
    [138] (E)
    [139]
    [140] Where
    [141] R a , R b , R c and R d are the same or different and represent an alkyl group, an aryl group, a cyclic alkyl group or a heterocyclic group which is bonded to a hydrogen atom, a halogen atom, directly or indirectly through a divalent linking group,
    [142] R e and R f are the same or different and represent a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carboxy group or a sulfo group.
    [143] (F)
    [144]
    [145] Where
    [146] X represents O or S,
    [147] R a , R b and R c are the same or different and represent an alkyl group, an aryl group or a cyclicalkyl group, optionally having a substituent which is bonded directly or through an oxy group, a thio group or an amino group,
    [148] Represents C = CC or CC = C.
    [149] (G)
    [150]
    [151] Where
    [152] X represents O or S,
    [153] R a , R b and R c are the same or different and represent an alkyl group, an aryl group or a cyclicalkyl group which optionally has a substituent which is bonded directly or through an oxy group, a thio group or an amino group,
    [154] R d represents an alkyl group or an aryl group,
    [155] Represents C = CC or CC = C.
    [156] (H)
    [157]
    [158] Where
    [159] R a and R b are the same or different and represent a hydrogen atom, an optionally substituted alkyl group, an aryl group or a heterocyclic group.
    [160] (Ⅰ)
    [161]
    [162] Where
    [163] R a , R b , R c and R d are the same or different and represent an alkyl group, an aryl group, a cyclic alkyl group or a heterocyclic group which is bonded to a hydrogen atom, a halogen atom, directly or indirectly through a divalent linking group.
    [164] (J)
    [165]
    [166] Where
    [167] R a , R b , R c and R d are the same or different and represent an alkyl group, an aryl group, a cyclic alkyl group or a heterocyclic group which is bonded to a hydrogen atom, a halogen atom, directly or indirectly through a divalent linking group,
    [168] R e represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carboxy group or a sulfo group.
    [169] In the above formulas (A) to (J), M represents a transition metal such as Ni, Pd, Pt, Cu, Co, etc., and may have a charge to form a salt with a cation, and another ligand above and below this M Can be combined. Such salts can also be used as light stabilizers. Examples of the alkyl group, cyclic alkyl group, aryl group, heterocyclic group, and substituents thereof in the formulas (A) to (J) include those mentioned above.
    [170] More preferred specific examples are shown in Table 2.
    [171] Table 2 Examples of Light Stabilizers for Metal Complexes
    [172]
    [173] 2) Aromatic amine light stabilizer (see Table 3)
    [174] The following compounds can be used.
    [175]
    [176] Where
    [177] R g , R h , R i and R j are the same or different and each represents a hydrogen atom or an alkyl group optionally having a substituent,
    [178] X represents an acid anion,
    [179] G is
    [180] m is 1 or 2 (p is 1 or 2), or
    [181] if m is 2 ,
    [182] Any aromatic ring present may be substituted by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a hydroxy group.
    [183] More preferred specific examples are shown in Table 3.
    [184] Table 3 Examples of Aminium, Immonium, or Dimonium Compounds
    [185]
    [186] c. Undercoat Layer
    [187] The undercoat layer includes (1) improved adhesion, (2) barriers such as water or gas, (3) improved storage stability, (4) improved reflectance, (5) protection of substrate from solvent, (6) Used for the purpose of forming guide grooves, guide feet, preformats, etc. For the purpose of (1), various polymers such as ionomer resin, polyamide resin, vinyl resin, natural resin, natural polymer, silicone, liquid rubber, and silane coupling agent can be used. For the purposes of (2) and (3), inorganic compounds such as SiO, MgF, SiO 2 , TiO, ZnO, TiN, SiN, etc. may be used in addition to the above polymer materials, and also metals or semimetals, for example For example, Zn, Cu, Ni, Cr, Ge, Se, Au, Ag, Al and the like can be used. In addition, for the purpose of (4), organic thin films having metals such as Al, Au, Ag, or metal luster, such as methine dyes, ultraviolet curing resins, thermosetting resins, and thermoplastic resins Etc. can be used.
    [188] The film thickness of the undercoat layer is preferably 0.01 to 30 µm, more preferably 0.05 to 10 µm.
    [189] d. Metal reflective layer
    [190] Examples of the metal reflective layer material include metals, semimetals, and the like that are not easily corroded, which exhibit high reflectances in themselves. Specific examples of the metal reflective layer material include Au, Ag, Cr, Ni, Al, Fe, Sn, and the like, and Au, Ag and Al are most preferred in view of reflectance and productivity. These metals or semimetals may be used alone or as two or more kinds of alloys.
    [191] As a film formation method, vapor deposition, sputtering, etc. are mentioned. The film thickness of the metal reflection layer is preferably 50 to 5,000 mm 3, more preferably 100 to 3,000 mm 3.
    [192] e. Protective layer, board surface hard coating layer
    [193] The protective layer and the substrate surface hard coating layer are intended to (1) protect the recording layer (reflective absorption layer) from scratches, dust and dirt, (2) improve the storage stability of the recording layer (reflective absorption layer), (3) improve the reflectance, etc. It is used as. For these purposes, the above-described undercoat layer material can be used. Further, as the inorganic material may be used, such as SiO, SiO 2, polymethyl acrylate, polycarbonate, polystyrene, polyester, vinyl resin, cellulose, aliphatic hydrocarbons, natural rubber is used as the organic materials, styrene-butadiene, chloroprene rubber, wax Thermosoftening resins such as alkyd, dry oil, rosin and the like; Thermosetting resins such as epoxy resins, phenol resins, polyurethane resins, melamine resins, urea resins, and the like; UV curable resins such as polyester acrylate, epoxy acrylate, urethane acrylate, silicone acrylate, and the like, and the like, and among these, UV curable resins can be preferably used in terms of excellent productivity.
    [194] It is preferable that it is 0.01-30 micrometers, and, as for the film thickness of a protective layer or a board | substrate hard coating layer, it is more preferable that it is 0.05-10 micrometers. In the present invention, the undercoat layer, the protective layer and the substrate surface hard coat layer may contain stabilizers, dispersants, flame retardants, lubricants, antistatic agents, surfactants, plasticizers and the like as described for the recording layer.
    [195] f. Protective board
    [196] The protective substrate should have transparency to the wavelength of the laser beam to be used when the laser beam is irradiated from the protective substrate side, but may or may not have transparency to be used simply as the protective plate. The materials that can be used are the same as the substrate materials, and plastics, glass, ceramics, or metals such as polyester, acrylic resins, polyamides, polycarbonate resins, polyolefin resins, phenol resins, epoxy resins, polyimide resins, and the like can be used. have.
    [197] g. Adhesive, adhesive layer
    [198] Any material can be used as long as it is a material capable of adhering two recording media. However, in view of productivity, an ultraviolet curable or hot-melt adhesive is preferable.
    [199] Best Mode for Carrying Out the Invention
    [200] Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
    [201] A. Synthesis of Squariarium Compounds
    [202] Example 1
    [203] 8.95 g of 3,4-dimethoxy-3-cyclobutene-1,2-dione and 12.74 g of 1-phenyl-3-propylpyrazolin-5-one were dissolved in 150 ml of methanol. 8.71 g of potassium carbonate was added to this solution, and the mixture was stirred at 25 ° C for 1 hour. After the reaction, the precipitate was collected by filtration. The obtained solid was added to a mixture of 3 g of potassium carbonate and 130 ml of water, and reacted at 50 ° C for 5 hours. When the reaction was completed, 100 ml of 1 mol / 1 hydrochloric acid aqueous solution was added and the insolubles were collected by filtration. 90 mL of n-butanol, 45 mL of toluene and 9.30 g of 5-chloro-1,3,3-trimethyl-2-methyleneindolin were added to the obtained solid, and the mixture was then treated at 110 ° C for 5 hours. Thereafter, 100 ml of methanol was added and the mixture was reacted at 80 ° C for 1 hour, after which the precipitate was collected by filtration. To the obtained solid, 175 ml of ethyl acetate, 17.5 ml of acetic acid and 4.97 g of aluminum tris (ethylacetoacetate) were added, reacted at 50 ° C for 2 hours, and the insolubles were collected by filtration to obtain 13.75 g of Compound 1.
    [204]
    [205] Example 2
    [206] 9.84 g of Compound 2 was obtained by the same method as Example 1 except for using 1-phenyl-3-isopropylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one.
    [207]
    [208] Example 3
    [209] 3.44 g of Compound 3 was obtained by the same method as Example 1 except for using 1-methyl-3-propylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one.
    [210]
    [211] Example 4
    [212] 1-phenyl-3-methylpyrazolin-5-one is used instead of 1-phenyl-3-propylpyrazolin-5-one, and instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin 0.68 g of Compound 4 was obtained by the same method as Example 1 except for using 1,3,3-trimethyl-2-methyleneindolin.
    [213]
    [214] Example 5
    [215] 0.99 g of Compound 5 was obtained by the same method as Example 1, except that 3-methyl-1-phenylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one.
    [216]
    [217] Example 6
    [218] 0.70 g of Compound 6 was obtained by the same method as Example 1 except for using 1-methyl-3-isopropylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one.
    [219]
    [220] Example 7
    [221] 4.23 g in the same manner as in Example 1, except that 2.65 g of 5-bromo-1,3,3-trimethyl-2-methyleneindolin was used instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin. Compound 7 was obtained.
    [222]
    [223] Example 8
    [224] 5.60 g of Compound 8 was obtained by the same method as Example 1, except that 3.76 g of 3-methyl-1- (3-methylphenyl) pyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one. It was.
    [225]
    [226] Example 9
    [227] 5.97 g of Compound 9 was obtained by the same method as Example 1, except that 3.76 g of 3-methyl-1- (4-methylphenyl) pyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one. It was.
    [228]
    [229] Example 10
    [230] 5.41 g of 1- (3-methylphenyl) -3-propylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one, 5-chloro-1,3,3-trimethyl-2 5.09 g of Compound 10 was obtained by the same method as Example 1 except that 3.59 g of 1,3,3-trimethyl-2-methyleneindolin was used instead of -methylene indoline.
    [231]
    [232] Example 11
    [233] 2.89 g of Compound 11 was obtained by the same method as Example 1 except for using 1.94 g of 1- (3-methylphenyl) -3-propylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one. It was.
    [234]
    [235] Example 12
    [236] 4.75 g of Compound 12 was obtained by the same method as Example 1 except that 5.41 g of 1- (4-methylphenyl) -3-propylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one. It was.
    [237]
    [238] Example 13
    [239] 2.61 in the same manner as in Example 1, except that 1.40 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin. g of compound 13 was obtained.
    [240]
    [241] Example 14
    [242] 7.33 g of Compound 14 in the same manner as in Example 1 except that 5.84 g of 1- (4-bromophenyl) -3-propylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one Obtained.
    [243]
    [244] Example 15
    [245] 5.84 g of 1- (4-bromophenyl) -3-propylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 5-chloro-1,3,3-trimethyl 5.48 g of Compound 15 was obtained by the same method as Example 1 except that 4.18 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of 2-methylene indoline.
    [246]
    [247] Example 16
    [248] 9.47 g of 1- (4-chlorophenyl) -3-methylpyrazolin-5-one is used instead of 1-phenyl-3-propylpyrazolin-5-one, and 5-chloro-1,3,3-trimethyl- 8.14 g of Compound 16 was obtained by the same method as Example 1 except that 4.60 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of 2-methylene indoline.
    [249]
    [250] Example 17
    [251] 14.22 g of Compound 17 was obtained by the same method as Example 1, except that 15.36 g of 1,3-diphenylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one.
    [252]
    [253] Example 18
    [254] 7.30 g of Compound 18 in the same manner as in Example 1, except that 13.31 g of 3- (4-methoxyphenyl) -3-phenylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one Obtained.
    [255]
    [256] Example 19
    [257] 7.72 g of Compound 19 was prepared by the same method as Example 1, except that 9.47 g of 1- (4-chlorophenyl) -3-propylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one. Obtained.
    [258]
    [259] Example 20
    [260] 7.72 g of Compound 20 was prepared in the same manner as in Example 1 except that 9.47 g of 1- (3-chlorophenyl) -3-propylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one. Obtained.
    [261]
    [262] Example 21
    [263] 9.12 g of 1-phenyl-3-trifluoromethylpyrazolin-5-one is used instead of 1-phenyl-3-propylpyrazolin-5-one, and 5-chloro-1,3,3-trimethyl-2- 3.87 g of Compound 21 was obtained by the same method as Example 1 except that 2.01 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of methylene indoline.
    [264]
    [265] Example 22
    [266] 5.29 g of 1- (3-chlorophenyl) -3-propylpyrazolin-5-one is used instead of 1-phenyl-3-propylpyrazolin-5-one, and 5-chloro-1,3,3-trimethyl- 7.56 g of Compound 22 was obtained by the same method as Example 1, except that 4.02 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of 2-methylene indoline.
    [267]
    [268] Example 23
    [269] 5.28 g of 1- (3-fluorophenyl) -3-propylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one, 5-chloro-1,3,3-trimethyl 8.94 g of Compound 23 was obtained by the same method as Example 1 except that 4.62 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of 2-methylene indoline.
    [270]
    [271] Example 24
    [272] 11.35 g of Compound 24 in the same manner as in Example 1, except that 5.28 g of 1- (4-fluorophenyl) -3-propylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one Obtained.
    [273]
    [274] Example 25
    [275] 4.44 g of a compound in the same manner as in Example 1, except that 2.16 g of 3-propyl-1- (4-trifluoromethylphenyl) pyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one 25 was obtained.
    [276]
    [277] Example 26
    [278] 8.35 g of 1- (4-chlorophenyl) -3-methylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 5-chloro-1,3,3-trimethyl- 9.51 g of Compound 26 was obtained by the same method as Example 1 except that 6.64 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of 2-methylene indoline.
    [279]
    [280] Example 27
    [281] 11.53 g of 1- (4-fluorophenyl) -3-methylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 5-chloro-1,3,3-trimethyl 11.00 g of Compound 27 was obtained by the same method as Example 1 except for using 7.08 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin, instead of 2-methylene indoline.
    [282]
    [283] Example 28
    [284] 2.16 g of 3-propyl-1- (4-trifluoromethylphenyl) pyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one, and 5-chloro-1,3,3- 1.22 g of Compound 28 was obtained by the same method as Example 1, except that 1.29 g of 1,3,3-trimethyl-2-methylene-4,5-benzoindolin was used instead of trimethyl-2-methylene indoline.
    [285]
    [286] Example 29
    [287] 1.70 g in the same manner as in Example 1, except that 1.02 g of 5-methoxy-1,3,3-trimethyl-2-methyleneindolin was used instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin. Compound 29 was obtained.
    [288]
    [289] Example 30
    [290] 4.04 g of Compound 30 was obtained by the same method as Example 1, except that 18.25 g of 1-phenyl-3-trifluoromethylpyrazolin-5-one was used instead of 1-phenyl-3-propylpyrazolin-5-one. .
    [291]
    [292] Example 31
    [293] 11.80 g of 1,3-dimethylparazoline-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 1 instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin 13.65 g of Compound 31 was obtained by the same method as Example 1, except that 18.25 g of, 3,3-trimethyl-2-methylene-4,5-benzoindolin was used.
    [294]
    [295] Example 32
    [296] 2.46 g of Compound 32 was obtained by the same method as Example 1 except that 1.72 g of 3,3-dimethyl-2-methylene indoline was used instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin.
    [297]
    [298] Example 33
    [299] 18.25 g of 1-phenyl-3-trifluoromethylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 5-chloro-1,3,3-trimethyl-2- 13.19 g of Compound 33 was obtained by the same method as Example 1 except that 9.71 g of 5-methoxy-1,3,3-trimethyl-2-methyleneindolin was used instead of methylene indoline.
    [300]
    [301] Example 34
    [302] 18.25 g of 1-phenyl-3-trifluoromethylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 5-chloro-1,3,3-trimethyl-2- 11.79 g of Compound 34 was obtained by the same method as Example 1, except that 9.20 g of 5-methyl-1,3,3,5-tetramethyl-2-methyleneindolin was used instead of methylene indoline.
    [303]
    [304] Example 35
    [305] 18.25 g of 1-phenyl-3-trifluoromethylpyrazolin-5-one instead of 1-phenyl-3-propylpyrazolin-5-one and 5-chloro-1,3,3-trimethyl-2- 12.34 g of Compound 35 was obtained by the same method as Example 1, except that 10.09 g of 1-methyl-2-methyleneindolin-3-spirocyclohexane was used instead of methylene indoline.
    [306]
    [307] Example 36
    [308] 0.70 in the same manner as in Example 1, except that 0.56 g of 5,7-dichloro-1,3,3-trimethyl-2-methyleneindolin was used instead of 5-chloro-1,3,3-trimethyl-2-methyleneindolin. g of compound 36 was obtained.
    [309]
    [310] B. Characterization of Squariarium Compounds
    [311] Example 37
    [312] The maximum absorption wavelength (λ max ) and the molar absorption coefficient at the maximum absorption wavelength of the chloroform solution of the compounds obtained in Examples 1 to 36 were measured. The results are shown in Table 4.
    [313] Example 38
    [314] The decomposition temperature of the compounds obtained in Examples 1 to 36 was measured. The results are shown in Table 4.
    [315] Comparative Example 1
    [316] Likewise, in Examples 1 to 6, the maximum absorption wavelength (λ max ) and the maximum absorption wavelength for the chloroform solution of the squariarium compound (compounds 1 b to 6 b ) prior to the metal complexation treatment (ie, not into the metal complex). The molar extinction coefficient at and the decomposition temperature were measured. The results are shown in Table 5.
    [317] Table 4 Spectroscopic Characteristics and Decomposition Temperatures of Squarium Compounds
    [318]
    [319] Table 4 (Continued) Spectroscopic Characteristics and Decomposition Temperatures of Squarium Compounds
    [320]
    [321] Table 5 Spectroscopic Characteristics and Decomposition Temperatures of Squarium Compounds
    [322]
    [323] Example 39
    [324] Optical constants of the compound thin films obtained in Examples 1 to 6 were measured. The results are shown in Table 6.
    [325] Comparative Example 2
    [326] Similarly, in Examples 1-6, the optical constant with respect to the squariarium compound (compound 1b- 6b ) thin film before metal complex treatment was measured. The results are shown in Table 7.
    [327] Table 6 Optical Constants of Squarium Compounds
    [328]
    [329] Table 7 Optical Constants of Squarium Compounds
    [330]
    [331] From Tables 6 and 7, it can be seen that a large refractive index was obtained by metal complexation, and solubility in an organic solvent was also improved.
    [332] Example 40
    [333] Xenon lamp light (50,000 lux) was irradiated to the compound thin film obtained in Example 1, 2 or 4, and the photo-deteriorating constant was measured from the change of optical density with time. The results are shown in Table 8. The photodegradation rate constant was calculated | required by the following formula.
    [334] d [OD] / d t = k [OD]
    [335] [OD]: Optical Density of Squarium Compound Thin Film
    [336] k: Photodegradation rate constant
    [337] Comparative Example 3
    [338] Similarly, in Example 1, 2 or 4, the photodegradation rate constant with respect to the squariarium compound (compounds 1b- 6b ) thin film before metal complexation treatment was measured. The results are shown in Table 8.
    [339] Table 8 Photodegradation Rate Constants of Squarium Compound Thin Films
    [340] Comparative Example Compounds / Example Compounds Photodegradation rate constant ratio: k 0 / kk 0 : Non-metal complex k: Metal complex 1 b / 1 7.2 2 b / 2 6.5 4 b / 4 5.8
    [341] From Table 8, it can be seen that the light resistance is improved by metal complexation.
    [342] C. Characterization of Optical Recording Media Using Squarium Compounds
    [343] An embodiment of an optical recording medium is described below.
    [344] Example 41
    [345] Compound 1 was prepared on 2,2,3,3-tetrafluoro-1-propanol on an injection molded polycarbonate substrate having a groove depth of 1,750 mm, a half band width of 0.38 μm and a track pitch of 0.74 μm. The solution dissolved in was spin-coated to form an organic dye layer having a thickness of 900 mm 3.
    [346] Subsequently, a gold reflective layer having a thickness of 1,200 Å was formed by the sputtering method, and a protective layer having a thickness of 7 μm was formed thereon with an acrylic photopolymer, and thereafter, an injection molded polycarbonate plate substrate having a thickness of 0.6 mm was adhered thereon with an acrylic photopolymer. To make an optical recording medium.
    [347] On the obtained optical recording medium, an EFM signal (speed of flux of 3.5 m / sec) was recorded while tracking using a semiconductor laser beam having an oscillation wavelength of 658 nm and a beam diameter of 1.0 μm, and then a semiconductor laser having an oscillation wavelength of 658 nm. It reproduced with the continuous beam (regeneration power 0.7 kW). The obtained signal characteristics are shown in Table 9.
    [348] Examples 42-46
    [349] An optical recording medium was formed in exactly the same manner as in Example 41 except that Compound 2, 3, 4, 5, or 6 was used instead of Compound 1, and signal characteristics were measured. The obtained signal characteristics are shown in Table 9.
    [350] Table 9 Signal Characteristics of Optical Recording Media
    [351] Reflectance (%): Groove Modulation Degree (%): I14 / I14H Jitter (%) Example 41 50 63.3 7.8 Example 42 49 63.7 8.0 Example 43 47 61.8 7.9 Example 44 48 62.9 8.0 Example 45 48 62.5 8.1 Example 46 49 63.1 8.3
    [352] It can be seen from Table 9 that the optical recording medium of the present invention obtains signal characteristics of high reflectance, high modulation and jitter in accordance with the DVD-R standard.
    [353] Example 47
    [354] An optical recording medium was formed using a mixture of compound 1 and metal complex 3 (see Table 2; weight ratio of compound 1 / metal complex = 10/3) instead of compound 1 in Example 41.
    [355] Xenon lamp (50,000 lux) was irradiated to this optical recording medium for 10 hours, and the residual ratio of optical density was evaluated. The residual ratio of optical density was calculated | required by the following formula.
    [356] Optical density residual ratio = I d / I 0 × 100 (%)
    [357] I d : optical density after light irradiation
    [358] I 0 : optical density before light irradiation
    [359] The obtained light resistance test results are shown in Table 10.
    [360] Examples 48-50
    [361] An aromatic amine compound 104 (see Table 3) (Example 48) was used instead of Metal Complex 3, and a mixture of Compound 2 and Metal Complex 12 (see Table 2) instead of the mixture of Compound 1 and Metal Complex 3 (Example 49). Alternatively, the optical recording medium was formed in the same manner as in Example 47 except that the mixture of Compound 2 and aromatic amine compound 113 (see Table 3) (Example 50) was used. The obtained light recording medium was subjected to the light resistance test in the same manner as in Example 47. The light resistance test results are shown in Table 10.
    [362] Table 10 Light resistance test results of optical recording media
    [363] Compound number Light Stabilizer Number Optical Density Retention Rate (%) Example 47 One 3 82 Example 48 One 104 89 Example 49 2 12 85 Example 50 2 113 91
    [364] Table 10 shows that the optical recording medium of the present invention exhibits excellent light resistance.
    [365] According to the present invention, it is possible to provide a squarium compound having optical and pyrolytic properties suitable for the oscillation wavelength of a semiconductor laser used in DVD-R. Further, by using the squariarium compound of the present invention as an optical recording material, it is possible to provide a DVD-R media having excellent light resistance and high reflectance and modulation.
    权利要求:
    Claims (12)
    [1" claim-type="Currently amended] Metal complex squariarium compounds of formula (I):

    Where
    R 1 and R 2 are the same or different and represent an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent, an aryl group optionally having a substituent or a heterocyclic group optionally having a substituent;
    Q represents a metal atom having coordination ability;
    q represents 2 or 3;
    A represents an aryl group optionally having a substituent, a heterocyclic group optionally having a substituent or Y = CH-, wherein Y represents an aryl group optionally having a substituent or a heterocyclic group optionally having a substituent.
    [2" claim-type="Currently amended] The metal complex type squariadium compound according to claim 1, wherein Y = CH- is formula (II):

    Where
    R 3 and R 4 are the same or different and represent an optionally substituted alkyl group, or R 3 and R 4 together with the adjacent carbon atoms may form an alicyclic hydrocarbon ring or a heterocycle optionally having a substituent;
    R 5 represents a hydrogen atom, an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent or an aryl group optionally having a substituent;
    R 6 represents a halogen atom, an alkyl group optionally having a substituent, an aralkyl group optionally having a substituent, an aryl group optionally having a substituent, a nitro group, a cyano group, or an alkoxy group optionally having a substituent;
    n represents an integer of 0 to 4;
    Herein, when n is 2 to 4, R 6 is the same or different, and two adjacent R 6 's may form an aromatic ring optionally having a substituent together with two adjacent carbon atoms.
    [3" claim-type="Currently amended] The metal complex type squariarium compound of Claim 1 or 2 whose Q is a trivalent metal.
    [4" claim-type="Currently amended] The metal complex type squariarium compound of Claim 3 whose trivalent metal is aluminum.
    [5" claim-type="Currently amended] An optical recording medium comprising a recording layer containing the metal complex type squariarium compound according to any one of claims 1 to 4.
    [6" claim-type="Currently amended] The optical recording medium according to claim 5, wherein the recording layer contains a light stabilizer.
    [7" claim-type="Currently amended] 7. The optical recording medium according to claim 6, wherein the light stabilizer is a compound selected from the group consisting of metal complexes and aromatic amines.
    [8" claim-type="Currently amended] 8. The optical recording medium according to claim 7, which contains 5 to 40% by weight of a light stabilizer based on the squariarium compound.
    [9" claim-type="Currently amended] 9. A recording layer monolayer of a recordable optical recording medium is in the range of 1.5≤n≤3.0 for light in a wavelength range of recording reproduction wavelength ± 5 nm. An optical recording medium having a refractive index n and an extinction coefficient k in a range of 0.02 ≦ k ≦ 0.3.
    [10" claim-type="Currently amended] 10. The track pitch according to any one of claims 5 to 9, wherein the track pitch on the substrate is in the range of 0.7 to 0.8 mu m, and the groove width is in the range of 0.18 to 0.40 mu m in half band width. Optical record carrier.
    [11" claim-type="Currently amended] The optical recording medium according to any one of claims 5 to 10, wherein the recording / reproducing wavelength is in the range of 600 to 700 nm.
    [12" claim-type="Currently amended] The light according to any one of claims 5 to 11, wherein the maximum absorption wavelength measured in the form of chloroform solution is in the range of 550 to 600 nm, and the logε (ε is the molar absorption coefficient) of 5 or more at this maximum absorption wavelength. Record carrier.
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    AT335050T|2006-08-15|
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    JP4065403B2|2008-03-26|
    JPWO2002050190A1|2004-04-22|
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    CN1330708C|2007-08-08|
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    EP1334998A4|2004-11-24|
    KR100766474B1|2007-10-15|
    EP1334998B1|2006-08-02|
    DE60121990T2|2007-03-08|
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-12-20|Priority to JP2000387192
    2000-12-20|Priority to JPJP-P-2000-00387192
    2001-12-19|Application filed by 교와 핫꼬 고교 가부시끼가이샤, 교와 유까 가부시키가이샤
    2002-12-31|Publication of KR20020097177A
    2007-10-15|Application granted
    2007-10-15|Publication of KR100766474B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000387192|2000-12-20|
    JPJP-P-2000-00387192|2000-12-20|
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