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    • 专利摘要:
    inkjet ink, inkjet etching method and ink etched material. an inkjet ink, which contains: water; a water-soluble organic solvent; a pigment; and particles of urethane resin and polycarbonate, wherein the water-soluble organic solvent contains 50% by mass or more of a diol compound, and wherein the water-soluble organic solvent contains 50% by mass or more of a soluble organic solvent in water having a boiling point of 200°C or less.
    公开号:BR112015018053B1
    申请号:R112015018053-1
    申请日:2014-01-27
    公开日:2021-09-14
    发明作者:Ichiroh Fujii；Naohiro Toda；Tomohiro Nakagawa；Hidefumi Nagashima；Juichi Furukawa
    申请人:Ricoh Company, Ltd；
    IPC主号:
    专利说明:

    Technical Field
    [0001] The present invention relates to an inkjet ink, which is most suitable for engraving on a base, an inkjet engraving method, and an ink engraved material. Background of the Technique
    [0002] Inkjet printers have advantages of low noise, low operating cost, ease of color printing, so they have been widely used in common households as a digital signal output device.
    [0003] In recent years, inkjet printers have been used for industrial use such as a screen, a poster or a bulletin board, as well as for home use. However, in the case of industrial use, a non-porous recording medium such as a plastic film has been used, because a porous recording medium has a disadvantage in terms of durability, such as lightfastness, resistance to light. water or wear resistance. Therefore, an ink for the non-porous recording medium was developed. For example, a solvent-based inkjet ink that contains an organic solvent as a vehicle and a UV-curable inkjet ink that contains a polymerizable monomer as a main ingredient have been widely used.
    [0004] However, solvent-based inkjet ink is not preferable from the point of view of environmental loads, as it vaporizes a large amount of solvent present there to the atmosphere. UV curable inkjet ink may have skin sensitization depending on the type of monomer being used. Furthermore, an expensive ultraviolet irradiation device must be integrated into a main body of a printer, which limits an ink application area.
    [0005] In view of the above-described background, recently an aqueous inkjet recording ink was developed to be able to be directly printed onto a non-porous base (see LPTs 1 and 2).
    [0006] However, it has been mentioned that aqueous ink is in some respects inferior to solvent based inkjet ink with regard to image quality.
    [0007] Firstly, non-porous base such as plastic film easily repels water, which is a main ingredient of aqueous ink, so that ink droplets ejected from a head do not easily wet and become spread over the base. As a result, micro-voids are left in a solid image, and high image density is difficult to achieve.
    [0008] Second, the ink basically does not penetrate into the non-porous base. Therefore, the ink ejected at the base must dry quickly. However, water that serves as the main solvent of the aqueous ink, and a water-soluble organic solvent that serves as an additive deteriorates a drying property of the ink, which tends to cause drying failure. Consequently, the passage of ink, called blocking, can occur when one printed material is placed on top of another or is rolled up.
    [0009] In addition, the non-porous foundation often has too much shine. Therefore, in order to prevent the integrity of an embossed material from being damaged between a printed portion and an unprinted portion while printing, an ink that can achieve a high gloss has been required. However, in the case of aqueous paint, unlike solvent-based paint in which resin is dissolved in the paint, the particles are fused together to thereby form a coating film, so that one surface of the paint tends to be rough and shine tends to be harmed.
    [00010] Furthermore, with regard to image fastness, scratch resistance and ethanol resistance were not achieved. So the fact is that an aqueous paint having superior performance is required.
    [00011] Meanwhile, an aqueous inkjet ink containing polycarbonate urethane resin particles was already known prior to patent application filing (see LPTs 3 and 4). However, a paint composition for the non-porous foundation was not examined. There were examinations only on conventional pigment inks.List of QuotationsPatent LiteratureLPT 1 Published Japanese Patent Application (JP-A) No. 2005-220352LPT 2 JP-A No. 2011-094082LPT 3 JP-A No. 2010-053328LPT 4 JP -A No. 2012-077118 Invention Summary Technical Problem
    [00012] An objective of the present invention is to provide an inkjet ink in which the droplets wet and spread over a base without leaving any empty spaces, which can achieve a high image density and gloss, which exhibits an excellent property drying, and which achieves high scratch resistance, ethanol resistance, and adhesive properties on a printed portion when ink is printed on the base. Solution to the problem
    [00013] One means of solving the above problems is as follows: an inkjet ink, which contains: water; a water-soluble organic solvent; a pigment; and polycarbonate urethane resin particles, wherein the water-soluble organic solvent contains 50% by mass or more of a diol compound, and the water-soluble organic solvent contains 50% by mass or more of a water-soluble organic solvent having a boiling point of 200°C or less. Advantageous Effects of Invention
    [00014] The present invention can solve the above problems, achieve the above objective, and provide an inkjet ink from which the drops wet and spread over a base without leaving gaps, which can achieve high image density and gloss, which exhibits excellent drying property, and which provides high scratch resistance, ethanol resistance, and adhesive property on a printed portion when ink is printed on the base.
    [00015] In particular, the inkjet ink of the present invention can provide an image having excellent gloss and image fastness when applied over a non-porous base such as a plastic film. Brief Description of Drawings
    [00016] FIG. 1 is a schematic diagram illustrating an example of a series-type inkjet recording device.
    [00017] FIG. 2 is a schematic diagram illustrating an example of a configuration in a main body of the ink jet recording device illustrated in FIG. 1. Modalities Description (Inkjet ink)
    [00018] An inkjet ink of the present invention (hereinafter may be referred to as an "ink") contains at least water, a water-soluble organic solvent, a pigment, and urethane and polycarbonate resin particles; and, if necessary, contain further ingredients.
    [00019] Inkjet ink contains a water-soluble organic solvent in order to prevent the ink from drying to a nozzle surface and to ensure the wettability of the ink onto a recording medium. Generally, a water-soluble organic solvent has a higher boiling point than water, so the water-soluble organic solvent does not dry out easily. Therefore, a water-soluble organic solvent having a relatively low boiling point must be used in order to achieve a required drying property in the present invention. However, when an organic solvent dries quickly, the resin particles usually prematurely form a film. As a result, a sufficiently uniform coating film cannot be formed, and the coating film is deteriorated in film strength and gloss.
    [00020] Therefore, the present inventors examined a relationship between the resin emulsion and a water-soluble organic solvent, and found that the polycarbonate and urethane resin particles allow a uniform film to be formed. Furthermore, they found that 50% by mass or more of the water-soluble organic solvent contained in the paint must be a diol compound; and 50% by mass or more, preferably 70% by mass to 90% by mass of the water-soluble organic solvent should be a water-soluble organic solvent having a boiling point of 200°C or less. When a content ratio of the diol compound or the water-soluble organic solvent having a boiling point of 200°C or less is less than 50% by mass, the resulting paint has a low drying property, so that it does not can form a satisfactory coating film and blockage is caused. <Urethane and polycarbonate resin particles>
    [00021] Urethane and polycarbonate resin is excellent in water resistance, heat resistance, wear resistance and weather resistance, due to the high cohesion of a carbonate group, so it is suitable for printed material used in a hostile environment like the outside. Urethane polycarbonate resin as used herein refers to a reaction product of polycarbonate and polyisocyanate polyol.
    [00022] As the polycarbonate-polyol, for example, those obtained through an interesterification reaction between the carbonate ester and polyol in the presence of a catalyst or those obtained through a reaction between bisphenol A and phosgene can be used .
    [00023] As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate or diphenyl carbonate can be used. As the polyol is reacted with the carbonate ester, for example, low molecular weight diol compounds such as ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1 ,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and 1,4-cyclohexanediol; polyethylene glycol; or polypropylene glycol can be used.
    [00024] Polyisocyanate is not particularly limited. Examples thereof include aromatic polyisocyanate compounds such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI ), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate , m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate; aliphatic polyisocyanate compounds such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanate methyl caproate, (2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-diisocyanatohexanoate; isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate and 2,6-norbornane diisocyanate. These can be used alone or in combination.
    [00025] A paint of the present invention is intended to be used for outdoor use, such as a poster or a sign, so that it is necessary to form a coating film having excellent weatherability over a long period of time. From this point of view, aliphatic or alicyclic diisocyanates are preferably used.
    [00026] Furthermore, a paint of the present invention preferably contains at least one alicyclic diisocyanate. In the case where the polycarbonate and urethane resin particles have structures derived from an alicyclic diisocyanate, the resulting paint is further improved in scratch resistance and ethanol resistance. Isophorone diisocyanate and dicyclohexylmethane diisocyanate are particularly preferred. A content ratio of alicyclic diisocyanate is preferably 60% by mass or more, with respect to the total content of isocyanate compounds.
    [00027] In a paint of the present invention, the urethane and polycarbonate resin particles are added in the form of a resin emulsion in which the urethane and polycarbonate resin particles are dispersed in an aqueous medium. The resin solids content in the resin emulsion is preferably 20% by mass or more. When the solids content is 20% by mass or more, there is no problem in formulating the resulting paint. The volume mean particle diameter of the urethane resin particles is preferably from 10 nm to 350 nm from the viewpoints of the storage stability and ejection stability of the resulting ink.
    [00028] When dispersing the urethane resin particles into the aqueous medium, forced emulsification using a dispersing agent can be used. In the case of forced emulsification, however, the dispersing agent can remain on a coating film to thereby decrease the strength of the same. Therefore, self-emulsifying urethane resin particles that have anionic groups in their molecular structure are preferably used. In the case where self-emulsifying urethane resin particles are used, it is preferable that the anionic groups are contained so that the acid value thereof is 20 mg KOH/g to 100 mg KOH/g, from the point of view of imparting excellent scratch resistance and chemical resistance.
    [00029] Examples of anionic groups include a carboxyl group, a carboxylate group, a sulfonic group, and a sulfonate group. Among them, a carboxylate group and a sulfonate group partially or fully neutralized with, for example, a basic compound are preferable from the point of view of maintaining good stability in aqueous dispersion. Examples of the basic compound that can be used to neutralize the anionic group include organic amines such as ammonia, triethylamine, pyridine and morpholine; alkanolamines such as monoethanolamine; and metal-based compounds that contain Na, K, Li, or Ca.
    [00030] In the case of forced emulsification using the dispersing agent, a nonionic surfactant and an anionic surfactant can be used as the dispersing agent. However, a non-ionic surfactant is preferable from the point of view of good water resistance.
    [00031] Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene alkyl ether, polyoxyethylene derivative, polyoxyethylene fatty acid ester, polyoxyethylene polyhydric alcohol fatty acid ester, polyoxyethylene propylene polyol, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene oil of hydrogenated castor, polycyclic phenyl ether polyoxyalkylene, polyoxyethylene alkylamine, alkylalkanolamide, and polyalkylene glycol (meth)acrylate. Among them, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkylamine are preferred.
    [00032] Examples of the anionic surfactant include alkyl sulfuric acid ester salt, polyoxyethylene alkyl ether sulfate, alkyl benzene sulfonate, -olefin sulfonate, methyl taurate, sulfosuccinate, ether sulfonate, ether carbonate, fatty acid salt, condensate of formalin sulfonate naphthalene, alkyl amine salt, quaternary ammonium salt, alkyl betaine, alkyl amine oxide α . Among them, preferably polyoxyethylene alkyl ether sulfate and sulfosuccinate.
    [00033] An amount of the added surfactant is preferably from 0.1% by mass to 30% by mass, more preferably from 5% by mass to 20% by mass, relative to that of said urethane resin. When the amount is 0.1% by mass or more, the surfactant can function as a dispersing agent. Meanwhile, the use of the surface-active agent in an amount of more than 30% by mass is not preferable, because an excessive amount, that is, an amount greater than necessary to form urethane resin emulsion, of an emulsifying agent significantly deteriorates adhesion capacity and water resistance. Also, plastification or breading is caused after drying of a coating film, so blocking tends to occur.
    [00034] Urethane and polycarbonate resin particles used in the present invention can be obtained through conventionally known production methods. An example of these includes the following method.
    [00035] Specifically, in the absence of a solvent or in the presence of an organic solvent, the polycarbonate polyol is reacted with the polyisocyanate in a ratio of equivalents so that the isocyanate groups are present in excess, to thereby produce a pre - Isocyanate-terminated urethane polymer. Then, the anionic groups of the isocyanate-terminated urethane prepolymer are optionally neutralized with the neutralizing agent, allowed to react with a chain extender, and finally, optionally, removing the organic solvent in one system.
    [00036] Examples of usable organic solvents include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; ester acetates such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; and amides such as dimethyl formamide, N-methylpyrrolidone and N-ethylpyrrolidone. These can be used alone or in combination.
    [00037] As for the chain extender, polyamines or other compounds containing an active hydrogen atom can be used.
    [00038] Examples of polyamines include diamines such as ethylene diamine, 1,2-propanediamine, 1,6-hexamethylene diamine, piperazine, 2,5-dimethyl piperazine, isophorone diamine, 4,4'-dicyclodiamine , 1,4- and cyclohexane diamine; polyamines such as diethylene triamine, dipropylene triamine and triethylene tetraamine; hydrazines such as hydrazine, N,N'-dimethylhydrazine, bishydrazine 1,6-hexamethylene; hyhydrazides such as disuccinic, adipic hyhydrazide, glutaric hyhydrazide, sebacic and diisophthalic hyhydrazide.
    [00039] Examples of other compounds containing an active hydrogen atom include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose , methylene glycol, glycerol and sorbitol; phenols, such as bisphenol A, 4,4'-hydroxydiphenyl, 4,4'-hydroxyphenyl ether, 4,4'-hydroxyphenyl sulfone, hydrogenated bisphenol A, and hydroquinone; and water. These can be used alone or in combination, as long as an ink of the present invention does not have deteriorated storage stability.
    [00040] An ink of the present invention contains polycarbonate and urethane resin particles with high heat resistance, so that the adhesiveness of the same can be improved by reducing a residual solvent by means of heat drying, after printing.
    [00041] The minimum filming temperature of polycarbonate and urethane resin particles may not necessarily be at or below room temperature. However, in the case where thermal drying is carried out after printing, the minimum film-forming temperature is preferably at least a temperature equal to or less than a temperature to which the ink is heated after printing, and especially preferably at a temperature sufficiently lower than the temperature to which the ink is heated. For example, when the paint is heated to 60°C, the minimum film-forming temperature of the resin is preferably from 0°C to 55°C, more preferably from 25°C to 55°C.
    [00042] Generally, the lower the minimum film-forming temperature, the better the film-forming property. However, when the minimum film-forming temperature is too low, the resin's glass transition temperature is also reduced, leading to unsatisfactory strength of the coating film.
    [00043] Note that the minimum film-forming temperature refers to a temperature at which a continuous transparent film is formed when the resin emulsion is cast onto a metal plate, such as aluminum, followed by heating. At a temperature range that is lower than the minimum film-forming temperature, the resin emulsion is in the form of a white powder.
    [00044] The polycarbonate and urethane resin particles used in the present invention preferably have a surface hardness at the time a coating film is formed of 100 N/mm2 or more, more preferably 120 N/mm2 to 180 N/mm2 . The surface hardness within the range described above allows the paint to form a hard coating film, which leads to greater scratch resistance.
    [00045] Surface hardness can be measured as follows.
    [00046] The emulsion of polycarbonate resin and urethane is applied on a glass slide so as to have a film thickness of 10 µm, followed by drying at 100 °C for 30 minutes to thereby form a resin film. The resulting resin film is measured to an indentation depth at the time a Berkovich indenter is indented with a load of 9.8 mN by means of a micro-surface hardness gauge (FISCHERSCOPE HM2000, product of Fischer Instruments KK) , and converted to a Martens hardness in accordance with ISO 14577-2002.
    [00047] An amount of polycarbonate and urethane resin particles added to the paint is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 8% by mass, even more preferably 3% by mass to 8% by mass of a solid content base. When the amount is 0.5% by mass or more, a coating film is sufficiently formed on a pigment, which leads to the desired image solidity. When the amount is 10% by mass or less, the resulting ink is not difficult to be ejected due to very high viscosity.
    [00048] The urethane and polycarbonate resin particles are added in the form of resin emulsion, along with other paint materials. The resin emulsion can contain, for example, a water-soluble organic solvent, an antiseptic agent, a lacquering agent, an antioxidant, a photostabilizer, and a UV absorber, if necessary.
    [00049] The paint of the present invention may contain resin particles other than urethane and polycarbonate resin particles. Examples of resin particles other than urethane and polycarbonate resin particles include acrylic resin particles, polyolefin resin particles, vinyl acetate resin particles, vinyl chloride resin particles, fluorinated particles, resin particles of polyether, and polyester resin particles.<Water-soluble organic solvent>
    [00050] A water soluble organic solvent used in the present invention must contain at least 50% by mass or more of a diol compound. The "diol compound" as used herein refers to a compound having two OH groups in its chemical structure. The diol compound has greater moisture holding capacity than a compound that has no or only one OH group, therefore, it significantly contributes to the resulting ink ejection reliability.
    [00051] A compound having three or more OH groups has very high intermolecular strength, so it often has an extremely high boiling point and significantly impairs a drying property of the resulting ink.
    [00052] Examples of the diol compound include ethylene glycol (PE: 196°C), propylene glycol (PE: 188°C), 1,2-butanediol (PE: 194°C), 2,3-butanediol (PE: 183 °C), 2-methyl-2,4-pentanediol (PE: 198 °C), diethylene glycol (PE: 244 °C), triethylene glycol (PE: 287 °C), dipropylene glycol (PE: 230 °C) , 1,3-propanediol (PE: 214°C), 1,3-butanediol (PE: 203°C), 1,4-butanediol (PE: 230°C), 2,2-dimethyl-1,3- propanediol (PE: 208 °C), 2-methyl-1,3-propanediol (PE: 213 °C), 1,2-pentanediol (PE: 206 °C), 2,4-pentanediol (PE: 201 °C ), 1,5-pentanediol (PE: 242 °C), 1,6-hexanediol (PE: 250 °C), 2-ethyl-1,3-hexanediol (PE: 243 °C), 1,2-hexanediol (PE: 224°C), and 2,5-hexanediol (PE: 217°C). These can be used alone or in combination.
    [00053] Fifty percent by mass or more of a water-soluble organic solvent used in the present invention must have a boiling point of 200 °C or less. Examples thereof include ethylene glycol (PE: 196°C), propylene glycol (PE: 188°C), 1,2-butanediol (PE: 194°C), 2,3-butanediol (PE: 183°C), 2-methyl-2,4-pentanediol (PE: 198 °C), dipropylene glycol monomethyl ether (PE: 190 °C), propylene glycol n-butyl ether (PE: 171 °C), propylene glycol ether t-butyl (PE: 153 °C), diethylene glycol methyl ether (PE: 194 °C), ethylene glycol-n-propyl ether (PE: 150 °C), and ethylene glycol-n-butyl ether (PE : 171°C). These can be used alone or in combination.
    [00054] The use of water-soluble organic solvent allows a paint having a high drying property on a non-porous base.
    [00055] Propylene glycol, 2,3-butanediol, or any combination thereof is preferably used as the water-soluble organic solvent having a boiling point of 200°C or less, because it is compatible with resin particles of urethane and polycarbonate and which can achieve a paint having an improved film-forming property. Thus, the above preferred water soluble organic solvents improve a gloss coating film.
    [00056] For the purpose of controlling the physical properties of the resulting paint, preventing the paint from drying out, and improving the stability of the paint in dissolution, a water-soluble organic solvent different from the water-soluble organic solvent having a boiling point of 200 °C or lower can be added if necessary.
    [00057] Examples of these include polyhydric alcohols such as diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3 -propanediol, 2-methyl-1,3-propanediol, 1,2-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, 1,2 - hexanediol, and 2,5 -hexanediol; polyhydric alcohol alkyl ethers, such as dipropylene glycol-n-propyl ether, tripropylene glycol methyl ether, tripropylene glycol-n-propyl ether, propylene glycol phenyl ether, triethylene glycol methyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, diethylene glycol-n-hexyl ether, and ethylene glycol phenyl ether; heterocyclic nitrogen containing compounds such as 2-pyrrolidone, N-methyl pyrrolidinone, and 1-ethyl-2-pyrrolidone; oxetane compounds such as 3-ethyl-3-hydroxymethyl oxetane.
    [00058] Among them, in addition to at least one selected from the group consisting of 3-ethyl-3-hydroxymethyl oxetane, tripropylene glycol monomethyl ether, and a water-soluble organic solvent containing a lactam structure and having a boiling point of 200 °C or more allows to achieve excellent properties such as image brightness, scratch resistance, ethanol resistance, in particular on a non-porous base. Furthermore, when 1-ethyl-2-pyrrolidone is added as a water-soluble organic solvent containing a lactam structure and having a boiling point of 200°C or more, excellent image quality can be achieved.
    [00059] Note that, a paint that contains no water-soluble organic solvent having a boiling point higher than 250 °C is further improved in a drying property, which is effective.<Pigment>
    [00060] As for the pigment, an inorganic pigment or an organic pigment can be used.
    [00061] Examples of inorganic pigments include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chromium yellow, and carbon black produced by a known method such as a contact method, furnace method, and thermal method. Examples of organic pigments include an azo pigment (eg, lacquered azo, an insoluble azo pigment, a condensed azo pigment, and a chelated azo pigment), a polycyclic pigment ( for example, a phthalocyanine pigment, a perylene pigment, a perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, an indigo pigment, a thioindigo pigment, an isoindolinone pigment, and a quinophthalone pigment), a chelate of dye (for example, a basic dye chelate and an acid chelate dye), a nitro pigment, a nitrous pigment, and aniline black.
    [00062] Among the above pigments, those which have a good affinity with a solvent are preferably used.
    Specific examples of preferable pigments for black include carbon blacks (CI Pigment Black 7), such as oven black, lamp carbon black, acetylene carbon black, and channel carbon black; metals such as copper, iron (Pigment Black Cl 11); metallic compounds such as titanium oxide; and organic pigments such as aniline black (Pigment Black Cl 1).
    [00064] Examples of pigments for colors include: Cl Pigment Yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 81, 83, 95 , 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 138, 150, and 153; CI Pigment Orange 5, 13, 16, 17, 36, 43 and 51; ClPigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48: 2, 48: 2 [Permanent Red 2B (Ca)], 48: 3, 48: 4, 49: 1.52 : 2, 53: 1, 57: 1 (Bright Carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81, 83, 88, 101 (colcothar), 104, 105, 106.108 (Cadmium red ), 112, 114, 122 (MagentaQuinacridone), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 209, and 219; CI Pigment Violet 1 (Lake Rhodamine), 3, 5:1, 16, 19, 23, and 38; CI Pigment Blue 1, 2, 15 (Phthalocyanine blue), 15: 1, 15: 2, 15: 3 (Phthalocyanine blue), 16, 17: 1, 56, 60 and 63; and CI Pigment Green 1, 4, 7, 8, 10, 17, 18 and 36.
    [00065] Furthermore, a self-dispersible pigment which is made dispersible in water by adding a functional group such as a sulfone group or a carboxyl group onto a surface of a pigment (eg carbon) can be used.
    [00066] Those that have been made water-dispersible by encapsulating a pigment in a microcapsule, ie resin particles containing pigment particles can also be used. In this case, all pigments incorporated in a paint are not necessarily encapsulated within or adsorbed onto resin particles. Pigments can be dispersed in the ink as long as the effects of the present invention are not impaired.
    [00067] A pigment particle diameter is not particularly limited and can be suitably selected depending on the intended objective, but is preferably from 20 nm to 150 nm, in terms of maximum frequency on the basis of maximum number. When the particle diameter is greater than 150 nm, the resulting ink is deteriorated in pigment dispersion stability, ejection stability, and image quality such as image density, which is not preferable. It is economically difficult to finely disperse the pigment so as to have the particle diameter less than 20 nm, because the dispersion operation or classification operation is complex.
    [00068] In the case where the pigment is allowed to be dispersed using a dispersing agent, appropriately selected conventionally known pigments can be used. Examples of these include a polymer dispersing agent and a water-soluble surface-active agent.
    [00069] An amount of pigment added to a paint is preferably about 0.1% by mass to about 10% by mass, more preferably 1% by mass to 10% by mass. Generally, as a pigment increases in concentration, the image density is increased to thereby improve image quality. Meanwhile, reliability such as reliability, ejection stability and clogging tend to be adversely affected. <water>
    [00070] In an inkjet ink of the present invention, pure water such as deionized water, ultra-filtered water, Milli-Q water, and distilled water, or ultra-pure water may be used. <Other ingredients>
    [00071] A paint of the present invention may, if necessary, contain other ingredients such as a surface-active agent, an antiseptic and antifungal agent, an anti-rust agent, or a pH regulator, in addition to water, the soluble organic solvent in water, the pigment, and the polycarbonate and urethane resin particles described above. <surfactant>
    [00072] Surfactant is added for the purpose of ensuring wettability in a recording medium. An amount of surfactant added to a paint is preferably 0.1% by mass to 5% by mass. When the amount is less than 0.1% by mass, the resulting ink has unsatisfactory wettability for a base, leading to degraded image quality. When the amount is greater than 5% by mass, the resulting ink cannot be ejected in some cases due to a high foam property.
    [00073] The type of surfactant is not particularly limited, and any of an ampholytic surfactant, a nonionic surfactant and an anionic surfactant can be used. However, preferably used are nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl amine, polyoxyethylene alkyl amide, polyoxyethylene-propylene glycol block polymer, fatty acid sorbitan ester, fatty acid sorbitan ester of polyoxyethylene, acetylene alcohol ethylene oxide adducts; and silicone surfactants, in view of a balance between dye dispersion stability and image quality.
    [00074] Silicone surfactant is not particularly limited and can be appropriately selected depending on the purpose for which it is intended. In particular, those that do not decompose even at high pH are preferable. Examples of these include side chain modified polydimethylsiloxane, either both end-modified polydimethylsiloxane, a end-modified polydimethylsiloxane, and both end-modified side-chain polydimethylsiloxane. Among them, particularly preferred are those which have a polyoxyethylene group or a polyoxypropylene polyoxyethylene group as a group to be modified, because they have excellent properties as an aqueous surfactant. As for the silicone surfactant, a polyether-modified silicone surfactant can be used. Examples thereof include a compound in which a polyalkylene oxide backbone is introduced into a side chain from a Si site in dimethylsiloxane.
    [00075] Other surfactants can be used in combination with silicone surfactant.
    [00076] Example of another surfactant includes a fluorosurfactant.
    [00077] Particularly preferred examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate ester compound, a perfluoroalkyl ethylene oxide adduct, and a polyoxyalkylene ether polymer compound containing a group perfluoroalkyl ether in its side chain, because of the low foaming property.
    [00078] Examples of the perfluoroalkyl sulfonic acid compound include perfluoroalkyl sulfonic acid, and perfluoroalkyl sulfonate. Examples of the perfluoroalkyl carboxylic acid compound include perfluoroalkyl carboxylic acid, and perfluoroalkyl carboxylate. Examples of the polyoxyalkylene ether polymer compound containing a perfluoroalkyl ether group in its side chain include polyoxyalkylene ether polymer sulfate ester salt containing a perfluoroalkyl ether group in its side chain polymer salt and polyoxyalkylene ether group containing a group perfluoroalkyl ether in its side chain. Examples of a counterion of a fluorine salt in the above fluorosurfactants include Li, Na, K, NH4, NH3CH2CH2OH, NH2(CH2CH2OH)2, and NH(CH2CH2OH)3. <Antifungal and antiseptic agent>
    [00079] Examples of antifungal and antiseptic agent include 1,2-benzisothiazoline-3-one, sodium benzoate, sodium dehydroacetate, sodium sorbate, sodium pentachlorophenol, and sodium 2-pyridinethiol-1-oxide. <Anti-rust agent>
    [00080] Examples of antirust agent include acid sulfite, sodium thiosulfate, ammonium thiodiglylate, diisopropyl ammonium nitrate, pentaerythritol tetranitrate, and ammonium dicyclonitrate. <pH regulator>
    [00081] The pH regulator can be any substance, as long as it does not adversely affect a paint to be prepared, and can adjust the pH of the paint to a desired value. Examples of the pH regulator include alkali metal element hydroxides (eg lithium hydroxide, sodium hydroxide and potassium hydroxide), alkali metal carbonates (eg lithium carbonate, sodium carbonate, and potassium carbonate) , quaternary ammonium hydroxide, amines (eg, diethanolamine, and triethanolamine), ammonium hydroxide, and quaternary phosphonium hydroxide.
    [00082] A paint of the present invention is produced by dissolving water, a water-soluble organic solvent, a pigment, polycarbonate resin particles and urethane, and, if necessary, other ingredients in an aqueous medium; and, optionally, stirring and mixing. Stirring and mixing can be carried out by means of an agitator equipped with a conventional impeller, a magnetic stirrer, or a high-speed disperser. (Inkjet recording method)
    [00083] An inkjet recording method of the present invention includes at least one step of jetting the ink which is a step of applying a stimulus (energy) to the inkjet ink of the present invention to allow it to the inkjet ink blasts to form an image on a base; and, if necessary, it can include further steps.
    [00084] Note that, the case where paper is used as a base will be described, but other porous bases or non-porous bases can also be used for engraving.
    [00085] Various known ink jet recording methods can be applied to the ink jetting step. For example, a scanning head-type inkjet recording method, or an inkjet recording method in which an image is recorded onto a certain sheet-shaped printing paper using aligned heads can be used.
    [00086] The recording head is generally used as an ink jetting unit in the ink jetting step. A recording head drive system is not particularly limited, and can be an on-demand head type, utilizing a piezoelectric element actuator using PZT, a system for operating thermal energy, or an actuator using electrostatic force; or a controllable charge head type of continuous jet type.
    [00087] An inkjet recording method of the present invention preferably includes a heat drying step, which is a step of drying a heat recording medium after printing, so as to form an image with a quality of higher image, scratch resistance, and tackiness, and to respond to high-speed printing conditions. A heating device used in the heat drying step can be appropriately selected from known devices. Examples of them include a device for forced air heating, radiation heating, conduction heating, high frequency drying, or microwave drying. These can be used alone or in combination.
    [00088] The heating temperature may vary depending on the type and amount of a water-soluble organic solvent contained in a paint, and the minimum film forming temperature of polycarbonate and urethane resin emulsion to be added, as well as a type of a base to be printed. The heating temperature is preferably high from the viewpoints of a drying property and a film-forming temperature. However, excessively high heating temperature is not preferable, as there is a possibility that the base to be printed will be damaged and the ink will not be ejected due to an increase in an ink head temperature. <Inkjet recording device>
    [00089] An inkjet recording device of the present invention includes at least one inkjet unit configured to apply a stimulus (energy) to the inkjet ink of the present invention to allow the ink to jet ink jet form an image on a base; and it also includes a heating unit, and, if necessary, other units.
    [00090] An inkjet recording device, which can perform recording using an inkjet ink of the present invention will be described with reference to the figures.
    [00091] Note that, the case where paper is used as a base will be described, but other porous bases or non-porous bases can also be used for engraving. The inkjet recording device includes a serial type inkjet recording device (carrier type) in which the transport is used for scanning, and a line type inkjet recording device which contains a line type head. FIG. 1 is a schematic diagram illustrating an example of a series-type inkjet recording device.
    [00092] This inkjet recording device contains a device main body 101, a paper feed tray 102 provided in the device main body 101, a paper discharge tray 103, and a cartridge loading section of ink 104. On an upper surface of the ink cartridge loading section 104, a control section 105, such as operating keys and screen are provided. The ink cartridge loading section 104 has a front cover 115 which can be opened and closed to place or remove an ink cartridge 200. Reference numeral 111 indicates a head cover, and 112 indicates a front surface of the front cover .
    [00093] In the main body of the device 101, as illustrated in FIG. 2, a carriage 133 is slidably held in a main scanning direction by a guide rod 131 which is a horizontal guide member bridged between the left and right side plates (not shown), and a support 132; and is moved for scanning by a main scan engine (not shown).
    [00094] A recording head 134 composed of four inkjet recording heads configured to eject yellow (Y), cyan (C), magenta (M) and black (BK) ink drops is installed on carriage 133 such that a plurality of ink ejection outlets are aligned in the intersecting direction of the main scanning direction and that the drop ink ejection direction is facing downwards.
    [00095] For each of the ink jet recording heads constituting the recording head 134, it is possible to use, for example, a head provided with one of the following ink ejection power generating units: a piezoelectric actuator, such as a piezoelectric element, a thermal actuator that uses a thermoelectric transducer, such as a heat element and uses phase change caused by the boiling film of a liquid, a shape memory alloy actuator that uses a phase shift of metal caused by a change in temperature, and an electrostatic actuator that uses electrostatic force.
    [00096] In addition, carriage 133 is provided with sub-tanks 135 for each color configured to supply each color of ink to recording head 134. Each sub-tank 135 is supplied and replenished with recording ink from from the loaded ink cartridge 200 to the ink cartridge loading section 104, through an ink supply tube (not shown).
    [00097] Meanwhile, as a paper feed section for feeding a base 142 loaded onto a base load section (pressurization plate) 141 of the paper feed tray 102, a crescent roller is provided. (paper roll feed 143) configured to feed the base 142 one by one of the base load section 141, and a separator block 144 which faces the paper feed roll 143, and is formed of a material with a large coefficient of friction. This separation block 144 is angled towards the side paper feed roller 143.
    [00098] As a conveyor section for transporting the base 142, which has been fed from that paper feeding section, under the recording head 134, a conveyor belt 151 is provided for transporting the base 142 by means of adsorption electrostatics; a counter roller 152 for carrying the base 142, which is sent from the paper feed section through a guide 145, while the base is sandwiched between the counter roller and the conveyor belt 151; a conveyor guide 153 for making the base 142, which is sent upwards in the substantially vertical direction, changes its direction by about 90°, whereby they run along the conveyor belt 151; and an end pressurizing roller 155 inclined to the side of the conveyor belt 151 by a pressure member 154. In addition, a loading roller 156 is provided which serves as a loading unit for loading a surface of the conveyor belt. 151.
    [00099] The conveyor belt 151 is an endless belt; and is capable of rotating about a conveyor belt direction by stretching between a heater-type conveyor roller 157 and a tension roller 158. The conveyor belt 151 has, for example, a surface layer which serves as a surface for adsorption of a non-porous base, which is formed from a resinous material [eg, ethylene-tetrafluoroethylene (ETFE) copolymer], with a thickness of approximately 40 μm for which resistance control was not accomplished; and a back layer (intermediate resistance layer, the soil layer) which is formed from the same material as the surface layer, and for resistance control, which was carried out using carbon. At the rear of the conveyor belt 151, a heater-like guide member 161 is placed correspondingly to a region where printing is effected by the recording head 134. Furthermore, as a paper discharge section for discharging the base 142 onto which images were recorded by recording head 134, a separating claw 171 is provided for separating base 142 from conveyor belt 151, a paper discharge roller 172, and a paper discharge roller 173 The base 142 is subjected to drying with hot air by means of an air heater 174, then being transmitted to the paper discharge tray 103 placed under the paper discharge roller 172.
    [000100] A double-sided paper feed unit 181 is detachably mounted on a rear surface portion of the main body of the device 101. The double-sided paper feed unit 181 receives the base 142 returned by belt rotation. conveyor 151 in the opposite direction and which reverses then feeds back into the middle of the counter roller 152 and the conveyor belt 151. In addition, a manual paper feed section 182 is provided on a top surface of the feed unit. double-sided paper 181.
    [000101] In the inkjet recording device, the base 142 is fed one by one from one by a paper feed section, and the base 142 fed upwards in the substantially vertical direction is guided by the guide 145 and transmitted with being sandwiched between the conveyor belt 151 and the counter roller 152. Furthermore, one end of the base is guided by the conveyor guide 153 and pressed onto the conveyor belt 151 for the pressurizing purpose of the roller 155, so that the transport direction of the base is changed by approximately 90°. At this time, the conveyor belt 157 is loaded by the loading roller 156, and the base 142 is electrostatically adsorbed onto the conveyor belt 151 and thus conveyed.
    [000102] Here, by directing the recording head 134 in accordance with an image signal by moving the carriage 133, ink drops are ejected into the base 142 having stopped in order to perform one-line recording. After that, the base 142 is transported a predetermined distance, and then recording of the next line is performed. upon receipt of a run recording signal or a signal indicating that a trailing end of the base 142 has reached a recording region, the recording operation is terminated, and the base 142 is discharged into the paper discharge tray 103. <Ink-Embossed Material>
    [000103] An ink-etched material of the present invention includes a base, and an image that is formed on the base using an inkjet ink of the present invention.
    [000104] The base is not particularly limited, and can be plain paper, gloss paper, specialty paper, or cloth. In particular, when the inkjet ink of the present invention is applied over a non-porous base, an image can be provided which has the good gloss and solidity of the image.
    [000105] Representative examples of non-porous base include those formed from a plastic material such as a transparent or colored film of polyvinyl chloride, polyethylene terephthalate (PET), polycarbonate film, acrylic film, polypropylene film, plastic film. polyimide, and polystyrene film; and which contains no paper components such as wood pulp paper, Japanese paper, synthetic cellulose paper and synthetic fiber paper. However, the ink of the present invention exhibits satisfactory performance on other non-porous bases and conventional porous media, such as plain paper or porous media coated with inorganic matter.
    [000106] The present invention will be further specifically described with reference to Examples and Comparative Examples, but it is not limited to Examples. Note that, "part(s)" described in the examples and comparative examples means "part(s) by mass", and the numerical values described in Tables 1-1 to 2 also mean "part(s) by mass. " <Preparation of polycarbonate and urethane resin emulsion A>
    [000107] A reaction vessel equipped with an agitator, a reflux condenser, and a thermometer, was charged with 1500 g of polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate), 220 g of acid 2 ,2-dimethylal propionic (DMPA), and 1.347 g of N-methylpyrrolidone (NMP) under a stream of nitrogen gas, followed by heating to 60 °C to thereby dissolve DMPA.
    [000108] Then 1.445 g of 4,4'-dicyclohexylmethane diisocyanate and 2.6 g of dibutyltin laurate (catalyst) were added thereto, followed by heating to 90 °C to allow for urethanization for 5 hours to thereby obtain an isocyanate-terminated urethane prepolymer.
    [000109] Then the resulting reaction mixture was cooled to 80 °C. For this, 149 g of triethylamine was added and mixed together, and 4.340 g of the resulting mixture was taken out and added to a mixed solution of 5400 g of water and 15 g of triethylamine with vigorous stirring.
    [000110] Then, 1,500 g of ice and 626 g of a 35% by mass solution of 2-methyl-1,5-pentanediamine acid in water were added to it, to allow, thus, a chain elongation reaction. The solvents were distilled off to give a solids content of 30% by mass, to thereby obtain an emulsion of urethane resin and polycarbonate A having a volume mean particle diameter of 25 nm. The volume mean particle diameter was measured by means of NANOTRAC WAVE-UT151 (product of NIKKISO CO., LTD.).
    [000111] This emulsion was applied on a glass slide so as to provide a film thickness of 10 µm, and dried at 100 °C for 30 minutes to form a resin film. The resulting resin film was taken to have a Martens hardness of 120 N/mm2 as measured by a micro surface hardness tester (FISCHERSCOPE HM2000, product of Fischer Instruments KK) at the time a Vickers indenter is indented with a load of 9.8 mN. <Preparation of polycarbonate and urethane resin emulsion B>
    [000112] An emulsion of urethane resin and polycarbonate B, having the volume average particle diameter of 20 nm was obtained in the same way as in the preparation of the emulsion of urethane resin and polycarbonate A, except that hexamethylene isocyanate was used, instead of 4,4'-dicyclohexylmethane diisocyanate. The volume mean particle diameter was measured by means of NANOTRAC WAVE-UT151 (product of NIKKISO CO., LTD.).
    [000113] The resulting emulsion B was taken to have a Martens hardness of 88 N/mm2, as measured for the strength of a coating film, in the same manner as emulsion A.<Preparation of polycarbonate urethane resin emulsion C>
    [000114] An emulsion of urethane resin and polycarbonate C having the volume mean particle diameter of 30 nm was obtained in the same way as in the preparation of the urethane resin and polycarbonate emulsion A, except that a mixture of isophorone diisocyanate and the diisocyanate of dodecamethylene (6:4 molar ratio) was used in place of 4,4'-dicyclohexylmethane diisocyanate. The volume mean particle diameter was measured by means of NANOTRAC WAVE-UT151 (product of NIKKISO CO., LTD.).
    [000115] The resulting emulsion C was taken to have a Martens hardness of 105 N/mm2, as measured for the strength of a coating film, in the same manner as emulsion A. <Preparation of pigment dispersion liquid 1>
    [000116] The materials described in the following formulation were previously mixed together, and then subjected to dispersion by circulation for 7 hours by means of a ball type disk mill (model KDL, products of SHINMARU ENTERPRISES CORPORATION, medium: ball of zirconia which has a diameter of 0.3 mm) to thereby obtain a pigment dispersion liquid 1. <Pigment Dispersion Liquid Formulation 1>
    [000117] Carbon black pigment (MITSUBISHI CARBONOBLOCK # 2300, product of Mitsubishi Chemical Corporation): 15 parts
    [000118] Anionic surfactant (PIONIN A-51-B, product of TAKEMOTO OIL & FAT Co., Ltd.): 2 parts
    [000119] Ion exchange water: 83 parts<Preparation of pigment dispersion liquid 2>
    [000120] A pigment dispersion liquid 2 was produced in the same manner as in the preparation of pigment dispersion liquid 1, except that the carbon black pigment was changed to pigment blue 15: 3 (HOSTAJET CIANO BG-PT, product of Clariant International Ltd.). <Preparation of pigment dispersion liquid 3>
    [000121] The liquid pigment dispersion 3 was produced in the same manner as in the preparation of the liquid pigment dispersion 1, except that the carbon black pigment was changed to Pigment Red 122 (HOSTAJET Magenta E-PT, product of Clariant International Ltd .).<Preparation of pigment dispersion liquid 4>
    [000122] A pigment dispersion liquid 4 was produced in the same manner as in the preparation of pigment dispersion liquid 1, except that the carbon black pigment was changed to Pigment Yellow 74 (Fast Yellow 7413, product of SANYO colors works, Ltd.).(Example 1)
    [000123] The materials described in the following paint formulation containing the pigment dispersion liquid 1 was mixed and stirred, and then filtered through a polypropylene filter, with an average pore diameter of 0.2 μm, to thereby produce a paint from Example 1.<Ink formulation>Pigment Dispersion Liquid 1: 20 parts Polycarbonate Urethane Resin Emulsion A: 15 parts Surfactant CH3(CH2)12O(CH2CH2O)3CH2COOH: 2 partsPropylene Glycol (PE: 188 °C ): 20 parts 3-ethyl-3-hydroxymethyl oxetane (PE: 240 °C): 15 parts PROXEL LV antiseptic-antifungal agent (product of Lonza Group AG): 0.1 parts Ion exchange water: 27.9 parts (Examples 2 to 19 and Comparative Examples 1 to 10)
    [000124] Each of the paints of Examples 2-19 and Comparative Examples 1 to 10 were produced in the same manner as in Example 1, except that the paint formulation was changed to the formulation described in each of the columns in Tables 1-1 to 1-3 (examples) and Tables 2-1 and 2-2 (comparative examples).
    [000125] Each of the paints was examined for their properties as follows. The results are shown in Tables 3-1 to 4. <Drying property>
    [000126] Each of the inks was loaded into an inkjet printer (IPSIO GXE5500, product of Ricoh Company, Ltd.), and a solid image was printed onto a gloss coated paper (OK TOP COAT +, product of Oji Paper Co., Ltd.), followed by drying at 25°C for a predetermined period. A filter paper was pressed against a post-drying solid piece with a load of 1 kg. Each of the inks was evaluated for drying property according to the following criteria based on the degree of transference of the ink to the filter paper. Note that, the drying property of grade 3.5 or more was considered acceptable.[Evaluation Criteria] Grade 5: Transfer to filter paper was not observed, after drying at 25°C for 10 min. Grade 4: Transfer to filter paper was not observed after drying at 25 °C for 20 min. Grade 3.5: Transfer to filter paper was not observed after drying at 25 °C for 30 min. Grade 3 : Transfer to filter paper was not observed after drying at 25 °C for 45 min.Grade 2: Transfer to filter paper was not observed after drying at 25 °C for 60 min.Grade 1: Transfer to paper filter was observed even after drying at 25 °C for 60 min. <Image brightness>
    [000127] Each of the inks was loaded into an inkjet printer (IPSIO GXE5500, product of Ricoh Company, Ltd.), and a solid image was printed onto PVC film (DGS-210-WH, product of Roland DG Corporation) which is a non-porous base, followed by drying at 80°C for 1 hour. Then, 60-degrees of gloss on a solid portion of the solid image was measured by a gloss meter (4501, BYK Gardener product).
    [000128] Note that at 60-degree brightness of 80 or more were considered acceptable.
    [000129] <Scratch resistance>
    [000130] Each of the inks was loaded into an inkjet printer (IPSIO GXE5500, product of Ricoh Company, Ltd.), and a solid image was printed onto PVC film (DGS-210-WH, product of Roland DG Corporation) which is a non-porous base, followed by drying at 80°C for 1 hour. Then, a solid portion of the solid image was scratched with a dry cotton cloth (KANAKIN No. 3) with a load of 400 g. The zero number was recorded at the time when a coating failure was visually observed. Risk numbers of 60 or more were considered acceptable. <Ethanol resistance>
    [000131] Each of the inks was loaded into an inkjet printer (IPSIO GXE5500, product of Ricoh Company, Ltd.), and a solid image was printed onto PVC film (DGS-210-WH, product of Roland DG Corporation) which is a non-porous base, followed by drying at 80°C for 1 hour. Then, a solid portion of the solid image was scratched with a cotton swab that had been impregnated with a 50% by mass solution of ethanol in water. The number of scratches was recorded at the time a coating failure was visually observed. Risk numbers of 30 or more were considered acceptable. <Ejection stability>
    [000132] Each of the inks was loaded into an inkjet printer (IPSIO GXE5500, product of Ricoh Company, Ltd.), which was supplied with a capping unit, and then left to stand for a week at a time. temperature of 30°C and a humidity of 15% RH with a head being covered. After that, a jet check pattern was printed, thus an occurrence rate (%) of non-ejection or injection disturbance was examined. An occurrence rate of 10% or less was considered to be acceptable. <Adhesive property>
    [000133] Each of the inks was loaded into an inkjet printer (IPSIO GXE5500, a product of Ricoh Company, Ltd.), and the solid images were printed on three bases: a PVC film (DGS-210-WH, product of Roland DG Corporation), a PP film (P2161, product of TOYOBO CO., LTD.), and a PET film (E5100, product of TOYOBO CO., LTD.), followed by drying thoroughly.
    [000134] Each of the solid parts of the solid images was evaluated for the number of peeled squares of 100 test squares by a cross-section of the test peel using a cloth tape (123LW-50, product of Nichiban Co., Ltd. .).
    [000135] Note that, the number of stripped squares of 5 or less than 100 test squares was considered to be acceptable.









    [000136] As can be seen from Tables 3-1 to 4, an aqueous inkjet ink containing polycarbonate resin particles and urethane, in which 50% by mass or more of the water-soluble organic solvent is a diol compound , and in which 50% by mass or more of the water-soluble organic solvent is a water-soluble organic solvent having a boiling point of 200°C or less has high drying property, and excellent image quality, resistance to scratches, ethanol resistance, ejection stability and adhesive property.
    [000137] As shown in Examples 1 to 6 and 9 to 13, the inclusion of at least one of propylene glycol and 2,3-butanediol in large amount achieves excellent ejection reliability. Furthermore, as shown in Examples 1 to 4, the inclusion of at least one selected from 3-ethyl-3-hydroxymethyl oxetane, tripropylene glycol monomethyl ether, and a water-soluble organic solvent containing a lactam structure and having a boiling point of 200 °C or more achieves, in particular, excellent scratch resistance and ethanol resistance.
    [000138] As shown in Examples 1 to 4, 7 and 10, and 12 to 16, the inclusion of urethane and polycarbonate resin particles having a structure derived from an alicyclic diisocyanate achieves, in particular, excellent scratch resistance and strength to ethanol.
    [000139] As shown in Examples 17 to 19, the inclusion of a silicone surfactant achieves, in particular, excellent image brightness while maintaining good adhesion properties.
    [000140] Embodiments of the present invention are as follows.
    [000141] <1> An inkjet ink, which contains: water; a water-soluble organic solvent; a pigment; and polycarbonate urethane resin particles, wherein the water-soluble organic solvent contains 50% by mass or more of a diol compound, and the water-soluble organic solvent contains 50% by mass or more of a water-soluble organic solvent having a boiling point of 200°C or less.
    [000142] <2> The inkjet ink according to <1>, wherein the water-soluble organic solvent having a boiling point of 200°C or less, at least one selected from the group consisting of propylene glycol and 2,3-butanediol.
    [000143] <3> The inkjet ink according to <1> or <2>, wherein the water-soluble organic solvent is at least one selected from the group consisting of 3-ethyl-3-hydroxymethyl oxetane , tripropylene glycol monomethyl ether, and a water-soluble organic solvent containing a lactam structure and having a boiling point of 200°C or more.
    [000144] <4> The inkjet ink according to <3>, wherein the water-soluble organic solvent containing the lactam structure is 1-ethyl-2-pyrrolidone.
    [000145] <5> The inkjet ink according to any one of <1> to <4>, wherein the water-soluble organic solvent is composed of a solvent with a boiling point of 250°C or less .
    [000146] <6> The inkjet ink according to any one of <1> to <5>, wherein each of the polycarbonate and urethane resin particles has a structure derived from at least one alicyclic diisocyanate.
    [000147] <7> The inkjet ink according to any one of <1> to <6>, wherein each of the polycarbonate and urethane resin particles has a surface hardness of 100 N/mm 2 or more at a time when a coating film is formed.
    [000148] <8> The inkjet ink according to any one of <1> to <3> and <5> to <7>, wherein the inkjet ink further contains a silicone surfactant.
    [000149] <9> An inkjet recording method, including: applying a stimulus to the inkjet ink according to any of the <1> <8> to enable the inkjet ink blast to thereby burn an image to a base.
    [000150] <10> The ink jet recording method according to <9>, wherein the ink jet recording method further includes heat drying the image after it has been recorded from having been recorded.
    [000151] <11> The inkjet recording method according to <9> or <10>, where the base is a non-porous base.
    [000152] <12> An ink-etched material, including: a base, and an image which is formed on the base with the inkjet ink according to any one of <1> <8>.
    [000153] <13> An ink-etched material in accordance with <12>, where the base is a non-porous base.
    [000154] <14> An inkjet recording device, including:an inkjet unit configured to apply a stimulus to the inkjet ink according to any one of <1> <8> to allow the inkjet ink blasts to thereby burn an image onto a base.
    [000155] <15> The inkjet recording device according to <14>, wherein the inkjet recording device further includes a heating unit configured to heat-dry the image after it has been recorded.
    [000156] <16> An ink cartridge, including:a container, and the inkjet ink according to any of the <1> <8> contained in the container.Signal Reference List101 Device Main Body102 Feed Tray Paper Dropping Tray104 Ink Cartridge Loading Section105 Control Section111 Head Cover112 Front Surface115 Front Cover131 Guide Rod 132 Bracket133 Loader134 Recording Head135 Sub-Tank141 Paper Loading Section142 Base143 Paper Feed Roller144 Separation Pad145 Guide151 Transport belt152 Counter roller153 Transport guide154 Pressure Member155 Pressurizing roller156 Load roller157 Carrier roller158 Tension roller161 Guide Member171 Separation jaw172 Paper Discharge Roll 173 Paper Discharge Roller 181 Double-Sided Paper Feed Unit182 Manual Paper Feed Section
    权利要求:
    Claims (12)
    [0001]
    1. Inkjet ink characterized by the fact that it comprises: water; a water-soluble organic solvent; a pigment; and polycarbonate urethane resin particles, wherein the water-soluble organic solvent comprises 50% by mass or more of a diol compound, and wherein the water-soluble organic solvent comprises 50% by mass or more of a water-soluble organic solvent having a boiling point of 200°C or less, wherein the water-soluble organic solvent having a boiling point of 200°C or less comprises propylene glycol, wherein the amount of propylene glycol added to the paint is 15% by mass and 20% by weight of the inkjet ink, and the water-soluble organic solvent having a boiling point of 200°C or less comprises 3-ethyl-3-hydroxymethyl oxetane.
    [0002]
    2. Inkjet ink according to claim 1, characterized in that the soluble organic solvent having a boiling point of 200 °C or less further comprises 2-3-butanediol.
    [0003]
    3. Inkjet ink according to claim 1, characterized in that the water-soluble organic solvent comprises 1-ethyl-2-pyrrolidone.
    [0004]
    4. Inkjet ink according to any one of claims 1 to 3, characterized in that the water-soluble organic solvent does not comprise a solvent with a boiling point of more than 250 °C.
    [0005]
    5. Inkjet ink according to any one of claims 1 to 4, characterized in that each of the urethane and polycarbonate resin particles has a structure derived from at least one alicyclic diisocyanate.
    [0006]
    6. Inkjet ink according to any one of claims 1 to 5, characterized in that each of the urethane and polycarbonate resin particles has a surface hardness of 100 N/mm2 or more at a time, when a coating film is formed, where the surface hardness is the Martens hardness determined in accordance with ISO14577-2002.
    [0007]
    7. Inkjet ink, according to any one of claims 1 to 2 and 4 to 6, characterized in that the inkjet ink further comprises a silicone surfactant.
    [0008]
    8. Inkjet recording method characterized in that it comprises: the application of a stimulus to the inkjet ink as defined in any one of claims 1 to 7 capable of allowing the inkjet ink to jet to in this way record an image on the base.
    [0009]
    9. Inkjet recording method according to claim 8, characterized in that the inkjet recording method further comprises drying by heat after the image is recorded.
    [0010]
    10. Inkjet recording method according to claim 8 or 9, characterized in that the base is a non-porous base.
    [0011]
    11. Ink-etched material characterized in that it comprises: a base, and an image which is formed on the base with the inkjet ink as defined in any one of claims 1 to 7.
    [0012]
    12. Ink-etched material, according to claim 11, characterized in that the base is a non-porous base.
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    JP6776648B2|2020-10-28|Ink, ink set, ink container, inkjet recording method, recording method, inkjet recording device, and recorded material
    JP6794623B2|2020-12-02|Ink and inkjet recording method
    JP6866734B2|2021-04-28|Printing method
    JP2018095841A|2018-06-21|Cleaning fluid, container, inkjet printing method, inkjet printing apparatus, and set of ink and cleaning fluid
    JP6358464B2|2018-07-18|Inkjet recording method and method for producing inkjet recorded product
    JP6740808B2|2020-08-19|Ink, inkjet recording method, and recorded matter
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    同族专利:
    公开号 | 公开日
    EP2951247A4|2015-12-16|
    RU2622312C2|2017-06-14|
    CN104968735B|2017-03-08|
    US20150361282A1|2015-12-17|
    JP2014198824A|2014-10-23|
    US9663668B2|2017-05-30|
    EP2951247B1|2018-10-24|
    JP6291841B2|2018-03-14|
    EP2951247A1|2015-12-09|
    CN104968735A|2015-10-07|
    WO2014119769A1|2014-08-07|
    RU2015136599A|2017-03-07|
    BR112015018053A2|2017-07-18|
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    法律状态:
    2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-29| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-09-14| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    2021-11-23| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 8A ANUIDADE. |
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    JP2013-015461|2013-01-30|
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    PCT/JP2014/052364|WO2014119769A1|2013-01-30|2014-01-27|Inkjet ink, inkjet recording method and ink recorded matter|
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