WO2003070841A1 - Composition d'encre et procede d'enregistrement d'image a jet d'encre - Google Patents

Composition d'encre et procede d'enregistrement d'image a jet d'encre Download PDF

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Publication number
WO2003070841A1
WO2003070841A1 PCT/JP2003/001715 JP0301715W WO03070841A1 WO 2003070841 A1 WO2003070841 A1 WO 2003070841A1 JP 0301715 W JP0301715 W JP 0301715W WO 03070841 A1 WO03070841 A1 WO 03070841A1
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group
polymer
ring
alkyl group
acid
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PCT/JP2003/001715
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English (en)
Japanese (ja)
Inventor
Nobuhiro Nishita
Junichi Yamanouchi
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Fuji Photo Film Co., Ltd.
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Publication of WO2003070841A1 publication Critical patent/WO2003070841A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers

Definitions

  • the present invention relates to an ink composition containing a film-forming composition for protecting a recorded image, capable of maintaining high image quality of an obtained image and improving image storability, particularly light fastness.
  • the present invention also relates to a method for recording an inkjet image using a composition for forming a film for protecting a recorded image.
  • the present invention relates to an ink jet image recording method using a polymer-fine particle dispersion suitable for forming a film on an obtained image and improving image storability.
  • Ink jet recording methods include a method in which pressure is applied by a piezo element to eject droplets, a method in which bubbles are generated in ink by heat to eject droplets, a method using ultrasonic waves, or a method using electrostatic force. There is a method of sucking and discharging droplets.
  • Ink jet recording inks of these types include water-based inks, oil-based inks, and solid inks.
  • JP-A-61-36636 and JP-A-2-212566 are each an ink jet containing a water-soluble virazolylazo dye for the purpose of achieving both hue and light fastness.
  • a recording ink is disclosed.
  • the dyes used in each publication have insufficient improvement in hue, and when used as a water-soluble ink, have insufficient solubility in water.
  • Japanese Patent Application Publication No. 11-509498 proposes, in addition to the dye structure similar to the above, a compound containing an interacting group and an ink composition.
  • Japanese Patent Application Publication No. 11-509498 proposes, in addition to the dye structure similar to the above, a compound containing an interacting group and an ink composition.
  • all of these inks for ink jet recording had poor hue, and under severe conditions such as long-term storage at a high temperature, image degradation might occur.
  • the image deterioration under such severe conditions is particularly remarkable in the image receiving paper containing the white inorganic pigment in the image receiving layer.
  • the image reacts with the white inorganic pigment itself and adsorbs to the white inorganic pigment. It is estimated that there is an effect of gas components.
  • JP-A-1-1770674 discloses an ink containing an ultraviolet absorber and Z or an antioxidant. Although a recording liquid for jetting is disclosed, it cannot be said that the quality of the obtained image is sufficient, and it has been desired to further improve the image storability.
  • Japanese Patent Application Publication No. 55-184412 discloses a method in which latex is contained in an ink composition and ejected from a recording head.
  • the coating effect is insufficient due to the deterioration of the dischargeability and the decrease in the amount of latex applied in the low-concentration areas.Also, it is effective for gases such as oxygen poison, but also improves the light resistance. Not enough.
  • a latex layer was provided on an alumina hydrate layer, and an image was formed on the alumina hydrate layer by ink. Later, a method of coating the latex layer is described. However, when the latex layer is heated and formed into a film by the above method, if the ink or solvent remains in the latex layer, cracks occur in the film, and the weather resistance and water resistance of the portion are reduced. The problem arises.
  • Japanese Patent Publication No. 113-133419 Japanese Patent Publication No. 113-133419
  • thermosetting resin coating or a radiation hardening resin coating on an image surface
  • the solvent in the paint may cause discoloration and discoloration of the image, promote the spread of the image, make it difficult to form a uniform coating film, and contaminate the coating solution during storage. And there is a problem that dust adheres at the time of application. In addition, the troublesome work of performing the coating had to be performed. Disclosure of the invention
  • an object of the present invention is to obtain an ink jet recorded image having high image quality and good image storability (water resistance, light resistance, weather resistance, etc.).
  • ⁇ a and b may have a substituent
  • Ar 1 is an aryl group or an aromatic heterocyclic group
  • -L 1 is a single bond or 10-
  • the benzene ring c may have a substituent.
  • the benzene ring d and the triazine ⁇ e may have a substituent; Another aromatic ring or hetero ring may be condensed to the benzene ring d.
  • the benzene rings f and g may have a substituent.
  • A is an aryl group or an aromatic heterocyclic group
  • R 1 is a hydrogen atom or an alkynole group
  • R 2 and R 3 are each independently a cyano group, —CO R 13 — COOR 14 , -CONR 15 16 — S 0 2 R 17 or 1 S 0 2 NR 18 R 19 , wherein R 13 to R 19 each independently represent a hydrogen atom, an alkyl group, a substituted alkyl group or Or 2 is bonded to R 3 to form a 5- or 6-membered ring.
  • R 4 and R 5 it it independently a hydrogen atom, an alkyl group or ⁇ Li one group, or; 4 and R 5 and are bonded, 5-membered ring or R 6 and are each independently a cyano group, —CO 20 , —C00R 21 , —CONR 22 R 23 , one S0 2 R 24 or —S0 2 NR 25 R 26 ; R 20 -R 26 are each independently a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group, or R 6 and R 7 are bonded to form a 5- or 6-membered ring; Form. -General formula (VII)
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group or an aryl group, or R 11 and R 12 are bonded to form a 5-membered or 6-membered ring.
  • benzene rings h and i may have a substituent; a benzene ring]! And i may be condensed with another aromatic ring or heterocyclic ring.
  • An ink jet image recording method comprising forming an image on an image receiving material using the ink composition described in 1 or 2 above.
  • a solution containing the polymer-microparticle dispersion is applied to the image receiving material.
  • An inkjet image recording method comprising a polymer having at least one selected from the group of compounds represented by formulas (I) to (VIII) described in 1 as a partial structure.
  • the ink composition After applying the solution containing the polymer-fine particle dispersion to the image receiving material, while the ink composition containing the colorant is in a state capable of passing through the polymer-fine particle dispersion, the ink composition is used.
  • An ink jet image recording method in which the polymer fine particle dispersion is ejected imagewise onto an image receiving material.
  • An ink jet image recording method comprising a polymer having at least one selected from the group of compounds represented by (VIII) as a partial structure.
  • the present invention is characterized in that a polymer-fine particle dispersion containing a polymer having a specific compound in a partial structure is used.
  • the polymer fine particle dispersion forms a film on the image, it is possible to improve the weather resistance and the water resistance of the recorded image against oxygen poison and heat. Further, since the polymer having the specific compound in the partial structure has an ultraviolet absorbing ability, the light fastness of an image can be improved.
  • the polymer fine particle dispersion may be used in the ink composition, or may be used as a separate liquid from the ink composition, and the ink and the polymer fine particle dispersion may be separately prepared. It may be provided on the image receiving material. In the latter case, it is easy to form a uniform film of the polymer fine particle dispersion on the image receiving material regardless of the concentration of the ink, so that a sufficient film effect can be obtained, gloss unevenness of the image can be prevented, and the image quality can be improved. it can.
  • the polymer fine particle dispersion (polymer latex) of the present invention is a product prepared by a so-called emulsion polymerization method using a vinyl monomer, in which the polymer is dispersed in a fine particle form in an aqueous medium.
  • the structure of the polymer constituting the polymer-fine particle dispersion may be a homopolymer of any monomer selected from the group of monomers shown below as typical examples or a copolymer of any combination thereof.
  • monomer unit that can be used, and any monomer can be used as long as it can be polymerized by a usual radical polymerization method.
  • a group of monomers that can be used, and any monomer can be used as long as it can be polymerized by a usual radical polymerization method.
  • Olefins ethylene, propylene, isoprene, butadiene, vinyl chloride, vinylidene chloride, 6-hydroxy-11-hexene, cyclopentene, 4-pentenoic acid, 8-nonenoic acid methyl, vinylsulfonic acid, trimethyl Vinylsilane, trimethoxyvinylsilane, butadiene, pendugen, isoprene, 1,4-divinylcyclohexane, 1,2,5-trivinylcyclohexane and the like.
  • alkyl acrylates eg, methyl acrylate, ethyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, substituted alkyl acrylate (eg, 2-chloroethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, arylacrylate), alkyl Methacrylates (eg, methyl methacrylate, n-butyl methyl acrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate), substituted alkyl methacrylates (eg, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin) Monomethacrylate, 2-a setokiche Rume evening
  • ethylene glycol diacrylate ethylene glycol dimethacrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylol propyl nonacrylate , Trimethicone acrylate triacrylate, dipentyl erythritol pentamethacrylate, dipentyl erythritol hexaacrylate,
  • Amides of a,? -unsaturated carboxylic acids for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N_methyl-N-hydroxyethylmethylacrylamide, N-tert-butylacrylic N-tert-octylmethacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxethyl) acrylamide, N-acryloylmorpholine, diacetone Acrylamide, itaconic acid diamide, N-methylmaleimide, 2-acrylamide-2-methylpropanesulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine, etc.
  • Styrene and its derivatives styrene, vinyltoluene, p-tert-butylstyrene, vinylbenzoic acid, methyl vinylbenzoate, paramethylstyrene, p-chloromethylstyrene, vinylnaphthalene, p-hydroxymethylstyrene, p-styrene Sodium sulfonate, potassium p-styrenesulfinate, 1,4-divinylbenzene, 4-vinylbenzoic acid-12-acryloylethyl ester and the like.
  • Vinyl ethers methyl vinyl ether, butyl vinyl ether, methoxethyl vinyl ether and the like.
  • Vinyl esters vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, and vinyl acetate.
  • the polymer synthesized by copolymerization of these monomers and preferably selected in the polymer fine particle dispersion of the present invention is mainly composed of acryl-methacrylic resin, styrene resin, conjugated diene resin, and vinyl acetate resin. And a homo- or copolymerized polymer such as polyolefin resin.
  • polymers having an ethylenically unsaturated group in the main chain or side chain that is, conjugated or at least two non-conjugated polymers It is more preferable that the polymer has an ethylenic unsaturated group and has at least two kinds of monomers having different polymerizabilities of the unsaturated groups as constituent monomer components, and particularly a polymer having a conjugated diene as a constituent component. preferable.
  • Monomers having at least two non-conjugated ethylenically unsaturated groups which are the preferred monomers described above, and monomers having different polymerizabilities of the respective unsaturated groups include aryl acrylate, aryl methacrylate, N-acrylate Rilacrylamide, N-arylmethacrylamide and the like can be mentioned.
  • Specific examples of conjugated diene monomers, which are particularly preferred monomers, include 1,3-butadiene, isoprene, 1,3-pentane, 2-ethyl-1,3-butadiene, and 2-n-propyldiene.
  • polymer fine particle dispersions may be used alone or in combination of two or more as necessary.
  • the emulsion polymerization method used for synthesizing the polymer fine particle dispersion of the present invention will be described below.
  • the emulsion polymerization method uses at least one emulsifier in water or a mixed solvent of water and an organic solvent miscible with water (eg, methanol, ethanol, acetone, etc.).
  • polymerization initiator examples include azobis compounds, peroxides, phenols, hydroxides, and redox catalysts, such as potassium persulfate and ammonium persulfate.
  • Inorganic peroxides such as t-butyl peroxide, benzoyl peroxide, isopropyl carbonate, 2,4-dichlorobenzene benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl Organic peroxides such as peroxides, 2,2,1-azobisisobutyrate, sodium salt of 2,2,1-azobiscyanovaleric acid, 2,2,1-azobis (2-amidinop mouth bread) Hide mouth Chloride, 2,2, -azobis [2- (5-methyl-2-imidazoline-1-yl) propane] hydrochloride, 2,2, -azobis ⁇ 2-methyl-N— [1,1,1-bis (hydroxy Methyl) -1-hydroxyethyl] propionamide ⁇ . Of these, potassium persulfate and ammonium persulfate are particularly preferred.
  • Emulsifiers include water-soluble polymers, in addition to anionic, cationic, amphoteric, and nonionic surfactants. Specific examples thereof include sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthylene sulfonate, sodium laurylbenzenesulfonate, lauryl Sodium phosphate, cetyl trimethylammonium chloride, N-2-ethylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxetylene sorbinyl lauryl ester, polyvinyl alcohol, Tokushou Sho 53
  • the emulsifier, water-soluble polymer and the like described in Japanese Patent No. 619090 are exemplified.
  • the polymerization reaction may be carried out by putting a monomer, a surfactant, and an aqueous medium in a reaction vessel in advance and adding an initiator, or, if necessary, any one of a monomer and an initiator solution. Alternatively, it may be carried out while dropping part or all of the two.
  • the polymer-fine particle dispersion of the present invention can be easily synthesized by using a conventional method of polymerization.
  • the general method of emulsion polymerization is detailed in the following books. "Synthetic Resin Emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Kobunshi Kanko (1978))", “Applications of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Keiji Kasahara, Keiji Kasahara, published by Takanoko Publishing (1993) ) "," Synthesis of Synthetic Latex (Munei Muroi) Issuance ())) ".
  • the polymer fine particle dispersion of the present invention especially what is known as soap free latex can be preferably used.
  • Another example of the polymer selected for the polymer-fine particle dispersion of the present invention is a water-insoluble polymer containing a dissociating group.
  • the water-insoluble polymer having a dissociating group refers to a polymer having an ionic dissociating group.
  • the ionic dissociating group includes a cationic dissociating group such as a tertiary amino group and a quaternary ammonium group, and an anionic dissociating group such as carboxylic acid, sulfonate and phosphoric acid.
  • polymer containing a dissociating group examples include vinyl polymers and condensation polymers (polyurethane, polyester, polyamide, polyurea, polycarbonate).
  • the water-insoluble polymer having a dissociating group is preferably a polymer having water dispersibility, that is, a polymer having a self-emulsifying property.
  • Examples of the dissociating group contained in the vinyl polymer having a dissociating group include a carboxyl group, a sulfonate group, Sulfuric acid monoester group, -OPO (OH) 2 , sulfinic acid group, or a salt thereof (for example, an alkali metal salt such as Na or K, or ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine)
  • Anionic groups such as ammonium salts such as amines and trimethylamines, or primary, secondary, and tertiary amines, or salts thereof (eg, organic acids (eg, acetic acid, propionic acid, methanesulfonic acid) and inorganic acids)
  • Examples include cationic groups such as acids (salts of hydrochloric acid, sulfuric acid, etc.) and quaternary ammonium salts. Groups are preferred, and carboxyl groups are particularly preferred.
  • Monomers containing the carboxylic acid as a dissociating group include, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl ester (for example, itaconic acid) Monomethyl, monoethyl itaconate, monobutyl itaconate, etc.) and monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.).
  • Examples of the monomer containing sulfonic acid as a dissociating group include styrene sulfonic acid, vinyl sulfonic acid, and acryloyloxyalkyl sulfonic acid (for example, For example, acryloyloxysulfonate, acryloyloxypropylsulfonate, etc., methacryloyloxyalkylsulfonate (eg, methacryloyloxysulfonate, methacryloyloxypropyl, etc.) Sulfonic acid, etc.), acrylamidoalkyl sulfonic acid (eg, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.) Acrylamidoalkylsulfonic acid (for example, 2-methylacrylamido-2-methylethanesulfonic acid
  • acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable, and acrylic acid, methacrylic acid, styrene sulfonic acid, and 2-acrylic acid are preferable.
  • Lilamide-2-methylpropanesulfonic acid and 2-acrylamide-2-methylbutanesulfonic acid are particularly preferred.
  • Examples of the monomer having a cationic dissociating group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl acrylate, and N-2-acryloyl. Monomers having a quaternary ammonium group, such as oxethyl-N, N, N-trimethylammonium chloride and N-vinylpentyl-N, N, N-triethylammonium chloride.
  • the above-mentioned monomer having a dissociating group may be copolymerized with a monomer having no dissociating group, and the following monomers can be used as the monomer. That is,
  • Acrylic esters specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl Tyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-acetoxitytyl acrylate, penzyl acrylate , Cyclohexyl acrylate, furfurino acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate Acrylate, 3-methoxy
  • Methacrylic acid esters specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate Plate, cyclohexyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl Methacrylate, 2-hydroxyethylmethacrylate, 4-hydroxybutyl methacrylate, triethyleneglycol / monomethacrylate, dipropylene glycol Nomethacrylate, 2-Methoxyethylmethacrylate,
  • Vinyl esters specifically, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl acetate, vinyl methoxyxia acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like.
  • Acrylamides specifically, acrylamide, methylacrylamide, ethylacrylamide, isopropylacrylamide, n-butylacrylamide, tert-butylacrylamide, tert-octylacrylamide, cyclohexylacrylamide, pendylacrylamide , Hydroxymethyl acrylamide, methoxymethyl acrylamide, butoxymethyl acrylamide, methoxethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, getyl acrylamide, ⁇ -cyanoethyl acrylamide, N- (2-acetoacetoxecilil ) Acrylamide, diaceton acrylamide and the like.
  • Methacrylamides specifically, methylacrylamide, methylmethylacrylamide, ethylmethylacrylamide, propylmethacrylamide, n-butylmethacrylamide, tert-butylmethylacrylamide, cyclohexylmethylacrylamide, benzylmethacryl Amide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, phenylmethacrylamide,? -Cyanoethylmethacrylamide, N- (2-acetoacetoxethyl) methacrylamide, etc.
  • Olefins specifically, dicyclopentene, ethylene, propylene,
  • Vinyl ethers specifically, methyl vinyl ether, butyl vinyl ether Hexylvinylether, methoxyethylvinylether, and the like.
  • Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, getyl maleate, dimethyl maleate, dibutyl maleate, getyl fumarate, dimethyl fumarate, dibutyl fumarate, and methyl vinyl ketone.
  • Phenylvinyl ketone methoxyethyl vinyl ketone, N-vinyloxazolidone, N-vinylpyrrolidone, vinylidene ore, methylenemalon nitrile, vinylidene and the like.
  • a monomer containing a nonionic dispersing group as described below.
  • examples of such a monomer include an ester of a polyethylene glycol monoalkyl ether and a carboxylic acid monomer, and a polyethylene glycol.
  • vinyl glycol monoalkyl ether and sulfonic acid monomer ester of polyethylene glycol monoalkyl ether and phosphoric acid monomer, vinyl group-containing urethane formed of polyethylene glycol monoalkyl ether and monomer containing isopropyl group, polyvinyl Examples include macromonomers having an alcohol structure.
  • the number of repetitions of the ethyleneoxy moiety of the polyethylene glycol monoalkyl ether is preferably from 8 to 50, and more preferably from 10 to 30.
  • the number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably from 1 to 20 and more preferably from 1 to 12.
  • the polyurethane containing a dissociating group is basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials.
  • diol compound examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, and non-dissociable diols.
  • diisocyanate examples include ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexanediisocyanate, and 2,4-toluene diisocyanate.
  • 1,3-xylylene diisocyanate 1,5-naphthylene diisocyanate, m-phenylene diisocyanate, p-phenylenediisocyanate, 3,3,1-dimethyl-1,4 , Diphenylmethane diisocyanate, 3,3,1-dimethylbiphenylene diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate) and the like.
  • the dissociable group-containing polyurethane can be obtained, for example, by using a diol containing a dissociable group during the synthesis of the polyurethane. In that case, the dissociating group is introduced into the polyurethane as a substituent from the polymer main chain.
  • diols having a dissociating group, particularly an anionic group examples include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid, and 2,5,6-trimethoxy-1,3,4-diene Examples thereof include hydroxyhexanoic acid, 2,3-dihydroxy-1,4,5-dimethoxypentanoic acid, 3,5-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid, and salts thereof.
  • the present invention is not limited to this.
  • the dissociating group contained in the dissociating group-containing polyurethane includes a carboxyl group, a sulfonate group, a sulfate monoester group, -OPO (OH) 2 , a sulfinic acid group, and a salt thereof (for example, Na, K, etc.).
  • Anionic groups such as alkali metal salts or ammonium salts such as ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine, trimethylamine, etc .; Cationic groups such as quaternary, tertiary amamine and quaternary ammonium salts are mentioned, and among them, anionic groups are preferable, and a carboxyl group is particularly preferable.
  • the dissociative group-containing polyester is basically synthesized by a condensation reaction between a diol compound and a dicarboxylic oxide compound.
  • dicarboxylic acid compounds include oxalic acid, malonic acid, succinic acid, glucuric acid, dimethyl malic acid, adipic acid, pimelic acid, hi, hi-dimethyl succinic acid, acetone dicarboxylic acid, sebacic acid, 1,9-nonanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-butylterephthalic acid, tetrachloroterephthalic acid, acetylene dicarboxylic acid Acid, poly (ethylene terephthalate) dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, ⁇ -poly (ethylene oxide) dicarboxylic acid, ⁇ -xylylenedicarboxylic acid, etc. Can be mentioned.
  • These compounds may be used in the form of an alkyl ester of dicarboxylic acid (eg, dimethyl ester) ⁇ ⁇ acid chloride of dicarboxylic acid when conducting a polycondensation reaction with a diol compound, or may be used in the form of maleic anhydride or succinic anhydride. It may be used in the form of an acid anhydride such as anhydrous hydrofluoric acid.
  • Dissociative group-containing polyesters include, in addition to carboxylic acids, sulfonic acid groups, monoester sulfate groups, - ⁇ ⁇ ( ⁇ ⁇ ) 2 , sulfinic acid groups, or salts thereof (for example, alkali metal salts such as ⁇ a and K). Or anionic groups such as ammonia, dimethylamine, ethanolamine, diethanolamine, triethanolamine, trimethylamine, etc.) or tertiary amines or salts thereof (eg, organic acids (eg, Acetic acid, propionic acid, methanesulfonic acid), inorganic acids (salts of hydrochloric acid, sulfuric acid, etc.) and quaternary ammonium salts.
  • the dissociating group other than the carboxylic acid contained in the dissociating group-containing polyester is preferably an anionic group, and particularly preferably a sulfonic acid group.
  • Preferred examples of the dicarboxylic acid and diol raw materials having a sulfonic acid group include sulfophthalic acids (3-sulfophthalic acid, 4-sulfophthalic acid, and 4-sulfoiso Fluoric acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid), sulfosuccinic acid, sulfonaphthylene dicarboxylic acids (4-sulfo 1,8-naphthylene dicarboxylic acid, 7-sulfo-1,5-naph Carboxylic acid), 3,5-di (2-hydroxy) ethyloxycarbonylbenzenesulfonic acid and salts thereof.
  • sulfophthalic acids (3-sulfophthalic acid, 4-sulfophthalic acid, and 4-sulfoiso Fluoric acid, 5-sulfoisophthalic acid, 2-sulfoterephthalic acid
  • diol compound a compound selected from the same group as the diols described in the above polyurethane can be used.
  • a typical synthetic method of the polyester is a condensation reaction of the diol compound with a dicarboxylic acid or a derivative thereof.
  • the condensation reaction of a hydroxycarboxylic acid such as a hydroxycarboxylic acid (for example, 12-hydroxystearic acid) is carried out.
  • ring-opening polymerization of cyclic ethers and lactones see Lecture Polymerization Theory (1) Takeo Saegusa (Chemical Doujin, 1991)).
  • the resulting polyester can also be suitably used in the present invention.
  • the dissociative group-containing polyamide can be obtained by polycondensation of a diamine compound and a dicarboxylic acid compound, polycondensation of an aminocarboxylic acid compound, or ring-opening polymerization of lactams.
  • diamine dani examples include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
  • Dicarboxylic acid Dicarboxylic acid, piperazine, 2,5-dimethylbiperazine, 4,4′-diaminodiphenyl ether, 3,3,1-diaminodiphenyl sulfone, xylylenediamine, etc., and aminocarboxylic acid Examples thereof include glycine, alanine, phenylalanine, ⁇ -aminohexanoic acid, ⁇ -aminodecanoic acid, ⁇ -aminoundecanoic acid, and anthranilic acid.
  • examples of monomers that can be used in ring-opening polymerization include: one-strand prolactam, azetidinone, and pyrrolidone.
  • dicarboxylic acid compound a compound selected from the same group as the dicarboxylic acids described in the polyester can be used.
  • the dissociative group-containing polyurethane can be obtained basically by polyaddition of a diamine compound and a diisocyanate compound or by a deammonification reaction of a diamine compound and urea.
  • the diamine compound as a raw material may be a diamine compound described in the above polyamide, and the diisocyanate compound may be a compound selected from the same group as the diisocyanate described in the above polyurethane.
  • the polycarbonate can be basically obtained by reacting a diol compound with a phosgene or a carbonate ester derivative (for example, an aromatic ester such as diphenyl carbonate). Compounds from the same group as the diols described in (1) can be used.
  • the dissociating group can be introduced into each of the polymers by various methods. For example, in the case of polyurethane, as described above, a diol containing a dissociating group can be used as a substituent from the polymer main chain by using it during synthesis. When a polyester is used, it can be introduced by leaving a dicarboxylic acid as an unreacted terminal at the terminal of the polymer.
  • a compound capable of introducing a dissociation group by a reaction such as an acid anhydride (for example, maleic anhydride) with a reactive group such as a hydroxy group or an amino group is introduced. You can also.
  • both the vinyl polymer and the condensed polymer may use one kind of necessary constituent material, or may be used for various purposes (for example, adjusting the glass transition temperature (T g) of the polymer).
  • T g glass transition temperature
  • solubility, compatibility with the dye, and stability of the dispersion can be used in any proportion.
  • those having at least one of a carboxyl group and a sulfonate group as the dissociating group are preferable, and those having a carboxy group as the dissociating group are particularly preferable.
  • the content of the dissociating group in the polymer containing a dissociating group is preferably from 0.1 to 3.0 mmol / g, more preferably from 0.2 to 2.0 mmolZg. If the content of the dissociating group is too small or too large, the self-emulsifying property of the dissociating group-containing polymer tends to be small, and the effect of stabilizing the polymer fine particle dispersion tends to be small.
  • the anionic dissociative group as the dissociative group may further be an alkali metal (for example, Na, etc.) or a salt of ammonium ion, and the like.
  • alkali metal for example, Na, etc.
  • a salt of ammonium ion and the like.
  • organic acids eg, acetic acid, Salts of propionic acid, methanesulfonic acid
  • inorganic acids such as hydrochloric acid and sulfuric acid
  • dissociative group-containing polymer in view of the above-mentioned dissociative group-containing polymer, in view of imparting excellent dispersion stability and ease of dissociation group introduction, more preferred are vinyl polymers, polyurethanes and polyesters, and particularly preferred is vinyl polymer.
  • condensation polymer among the polymers having a dissociating group are listed in Table 3 below, but the present invention is not limited thereto. Acidity in each polymer
  • the glass transition temperature Tg of the polymer constituting the polymer fine particle dispersion of the present invention is preferably from 140 ° C to 160 ° C.
  • the polymer fine particle dispersion of the present invention has at least one compound represented by the following general formulas (I) to (VIII) having an ultraviolet absorbing ability (hereinafter also referred to as an ultraviolet absorbing monomer) as a partial structure.
  • the polymer is included.
  • the partial structures of the compounds represented by formulas (I) to (VIII) preferably exist as side chains of the polymer.
  • the benzene groups a and b may have a substituent.
  • substituents include a halogen atom (F, Cl, Br), a nitro group, a cyano group, a sulfo group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a heterocyclic group, — 0- R, one S - R, one CO - R, one CO - 0 - R, one 0- CO- R, one SO -: R, one S0 2 - R, one NR 2, one NH- CO - R, one Topic - S0 2 - R, one CO- NR 2, one S0 2 - NR 2 -, includes single NH- CO- 0- R and single NH- CO- NR 2.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, Or a substituted alkenyl group or an aryl group.
  • the alkyl group contained in the ultraviolet absorbing monomer of the present invention preferably has 1 to 20 carbon atoms.
  • a chain alkyl group is preferred over a cyclic alkyl group.
  • the chain alkyl group may have a branch.
  • alkyl groups include methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl, 2-ethylhexyl, tert-octyl, decyl, Includes dodecyl, hexadecyl, octadecyl, cyclopropyl, cyclopentyl, cyclohexyl and bicyclo [2,2,2] octyl.
  • the alkyl part of the substituted alkyl group contained in the ultraviolet absorbing monomer of the present invention is the same as the above alkyl group.
  • substituent of the substituted alkyl group include an aryl group, one 0—R, —S—R, one CO—R, —CO—0—R, one 0—CO—R, one SO—one S0 2 - R, -N 2 _NH - CO- R, -NH-S0 2 -R, one CO- NR 2, one S0 2 _NR 2 -, - NH- CO- 0- R and single NH- CO- NR 2 is included.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • the alkenyl group contained in the ultraviolet absorbing monomer of the present invention preferably has 2 to 20 carbon atoms.
  • a chain alkenyl group is preferable to a cyclic alkenyl group.
  • the chain alkenyl group may have a branch. Examples of alkenyl groups include aryl, 2-butenyl, 2-butenyl and oleyl.
  • the alkenyl part of the substituted alkenyl group contained in the ultraviolet absorbing monomer of the present invention is the same as the above alkenyl group.
  • substituent of the substituted alkenyl group include an aryl group, 10-R, one S-R, one CO-R, -CO-0-Rs one 0-CO-R, one SO-R, one S0 2 _R, one NR 2, one NH- CO - R, one NH- S0 2 -R, one C0-N 2 _S0 2 -NR 2 -, one NH- CO- 0 - R and _NH - CO - NR 2 is included.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • the number of carbon atoms of the aryl group contained in the ultraviolet absorbing monomer of the present invention is 6 to Preferably it is 10.
  • aryl groups include phenyl and naphthyl.
  • the aryl group may have a substituent.
  • the substituent of the aryl group include an alkyl group, a substituted alkyl group, an aryl group, —0—R, —S—R, —CO—R, —CO—0—R, —0—CO—R, — SO_R, one S0 2 — R, — NR 2 , one NH-CO-R.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • the heterocyclic group contained in the ultraviolet absorbing monomer of the present invention preferably has a 5- or 6-membered heterocyclic group.
  • the heterocyclic ring include a furan ring, a thiophene ring, an indole ring, a pyrroyl ring, a birazol ring, an imidazole ring and a pyridine ring.
  • the heterocyclic group may have a substituent.
  • Examples of the substituent of the heterocyclic group include an alkyl group, a substituted alkyl group, an aryl group, —O—s—S_R, —C0—R, —C0—O—Rs—0—CO—R, and one SO - R, one S0 2 - R, one NR 2, one NH - C 0- R, -NH- S0 2 -Rs one CO- NR 2, one S0 2 - NR 2 -, one NH- CO - 0_R and single NH—CO—NR 2 included.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • Ar 1 is an aryl group or an aromatic heterocyclic group, and c A is preferably an aryl group.
  • the aromatic heterocyclic group preferably has a 5- or 6-membered heterocyclic ring.
  • the aromatic heterocyclic ring include a furan, thiophene, indole, pyrrolyl, pyrazole, imidazole and pyridine ring.
  • the aromatic heterocyclic group may have a substituent.
  • Examples of the substituent of the aromatic heterocyclic group include an alkyl group, a substituted alkyl group, an aryl group, 10-11, —S_R, -CO-R, one CO-0-R, one 0- CO - R, one SO - R, one S0 2 - H, one NR 2, one NH - CO- R, one NH- S_ ⁇ 2 - R, one CO - NR 2, one S0 2 - NR 2 -, one NH- CO- 0- R and single NH- CO- include NR 2.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • 1 L— is a single bond or 10 —.
  • One L1 is preferably a single bond.
  • the benzene ring c may have a substituent.
  • substituents include a halogen atom (F, Cl, Br), a nitro group, a cyano group, a sulfo group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a heterocyclic group, R, - S - R, one CO - R, one CO - 0 - R, one 0 - CO - R ⁇ one SO- R, - S0 2 - R , one NR 2, one NH- CO - R, one NH - S0 2 - R, one CO- NR 2, one S0 2 - NR 2 -, includes single NH- CO- 0- R and single NH- CO- NR 2.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a
  • the benzene ring d and the triazine ring e may have a substituent.
  • substituents include a halogen atom (F, Cl, Br), a nitro group, a cyano group, a sulfo group, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, and a heterocyclic group.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • the substituent on the triazine ring e is preferably an aryl group, more preferably phenyl, and most preferably 0-hydroxyphenyl.
  • another aromatic ring or hetero ring may be condensed to the benzene ring d.
  • the condensed aromatic ring include a benzene ring and a naphthylene ring.
  • the condensed heterocyclic ring include a furan ring, a thiophene ring, an indole ring, a vinyl ring, a pyrazolyl ring, an imidazole ring and a pyridine ring.
  • a benzene ring: f and g are each an optionally substituted c- substituent such as a halogen atom (F, Cls Br), a nitro group, a cyano group, a sulfo group.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • Ar 2 is an aryl group or an aromatic heterocyclic group.
  • the aromatic heterocyclic group preferably has a 5- or 6-membered heterocyclic group.
  • Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, an indole ring, a virole ring, a pyrazole ring, an imidazole ring and a pyridine ring.
  • the aromatic heterocyclic group may have a substituent.
  • substituent of the aromatic heterocyclic group include an alkyl group, a substituted alkyl group, an aryl group, one 0-R, one S-R, one CO-R, one CO-0-R, one 0-CO - R, one SO - R, one S0 2 - R, one NR 2, -NH-C0-R , one NH- S0 "R, one CO- NR 2, one S0 2 - NR" ⁇ - NH- CO- 0—R and —NH—CO—NR 2.
  • the above R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • R 1 is a hydrogen atom or an alkyl group.
  • R 2 and R 3 each independently represent a cyano group, —CO R 13 , one C00R 14 , one CONR 15 R 16 , one S 0 2 R 17 or one S 0 2 NR 18 R 19 , R 13 , R 14 , R 15 , RR 17 , R 18 and R 19 are each independently a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group; or , R 2 and R 3 combine to form a 5- or 6-membered ring. At least one of R 15 and R 16 is preferably a hydrogen atom. At least one of R 18 and H 19 is preferably a hydrogen atom.
  • 5- or 6-membered ring R 2 and R 3 is formed by bonding preferably functions as an acid nucleus in the methine dyes.
  • Examples of a 5- or 6-membered ring that functions as an acidic nucleus include a 2_birazolin-5-one ring, a birazolidine-1,2,4-dione ring, a mouth-danine ring, a hydantoin II, a 2-thiohydantoin ring, and a 4-thiothione ring.
  • Hydantoin ring 2,4-oxazolidinedione ring, isoxazolone ring, barbituric acid ring, thiobarbidyl acid ring, indandione ring, hydroxypyridone ring, furanone ring, Includes 1,3-cyclohexanedione ring and Meldrum's acid ring.
  • 5- or 6-membered ring R 2 and R 3 formed by bonding may have a substituent.
  • substituents on the 5- or 6-membered ring include alkyl, substituted alkyl, aryl, —0—11, one S—R, one CO—R, —CO—0—R, one 0 - CO- R ⁇ -SO-Rs one S0 2 _R, -N 2, one NH - CO -:, one NH- S0 2 - R, - CO - NR 2, one S0 2 - NR 2 -, one NH - CO- 0_R and single NH - CO- NR 2 is included.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • R 4 and R 5 are each independently a hydrogen atom, an alkyl group or an aryl group, or R 4 and R 5 are bonded to form a 5-membered ring or Form a 6-membered ring.
  • Examples of 5- or 6-membered ring and R 4 and R 5 are formed by bonding a pyrrolidine ring, a piperidine ring and morpholine ring.
  • 5- or 6-membered ring and R 4 and R 5 are formed by bonding may have a substituent.
  • substituents include alkyl, substituted alkyl, aryl, 1_R, -S-Rs-CO-R, 1C0_0-R, -0-CO-R, one SO- R, one S0 2 - R, - NR 2 , one NH- CO- R, one NH- S0 2 - R, one C0-N 2 one S0 2 - NR 2 -, one NH- CO- O- R and single NH- CO- NR 2 is included.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • R 6 and R 7, which it independently, Shiano group, -CO R 2 one C00R 21, one CONR 22 R 23, one S 0 2 R 24 or a S 0 2 NR 25 R 26 and R 2 .
  • R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are each independently a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group, or R 6 and R 7 Combine to form a 5- or 6-membered ring.
  • at least one of R 23 is preferably a hydrogen atom.
  • At least one of R 25 and R 26 is preferably a hydrogen atom.
  • 5- or 6-membered ring and R 6 and R 7 are formed by combining preferably functions as an acid nucleus in the methine dyes.
  • a 5- or 6-membered ring that functions as an acidic nucleus include 2-pyrazolin-1-5-one ring, virazolidine-1, 4-dione, lipo-danin II, hydantoin ring, 2-thiohydantoin ring, and 4-1 Thiohydantoin ring, 2,4-oxazolidinedione ring, isoxoxazolone ring, barbituric acid ring, thiobarbituric acid ring, indandione ring, hydroxypyridone ring, furanone ring, 1,3-cyclohexanedione ring and Includes Meldrum acid rings.
  • 5- or 6-membered ring and R B and R 7 are formed by bonding may have a substituent.
  • substituents include alkyl, substituted alkyl, aryl, 1—R, —S—R, —CO—R, —CO—0—R, — CO-R ⁇ one SO— R, one S0 2 -R ⁇ one NR 2 , one NH—CO—R, one NH— S0 2 — R, one CO— NR 2 , one S0 2 — NR 2 —, one NH- CO - 0 - include R and single NH- CO- NR 2.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • R 8 is an alkyl group, a substituted alkyl group or an aryl group.
  • R 9 and R 1Q each independently represent a cyano group, one COR 27 , one COOR 28 ⁇ one CONR 2S R 3 . , One S 0 2 R 31 or one S 0 2 NR 32 R 33 , wherein R 27 , R 28 , R Z9 , R 30 , RR 32 and R 33 each independently represent a hydrogen atom, an alkyl group, Is a substituted alkyl group or aryl group, or: 9 and R 10 combine to form a 5- or 6-membered ring. At least one of R and R 3Q Is preferably a hydrogen atom. At least one of R 32 and R 33 is preferably a hydrogen atom.
  • 5- or 6-membered ring and R 9 and R 1D is formed by bonding preferably functions as an acid nucleus in the methine dyes.
  • 5- or 6-membered rings that function as acidic nuclei include 2-virazoline-1-5-one ⁇ , virazolidine-1,2,4-dione, rhodanine ⁇ , hydantoin 2, 2-thiohydantoin 4, and 4-onethione.
  • Hydantoin ⁇ , 2,4-oxazolidinedione ring, isooxazolone ring, barbidyl acid ⁇ , thiobarbituric acid ring, indandione ring, hydroxypyridone ring, furanone ring, 1,3-cyclohexanedione ring and Meldrum's acid Rings are included.
  • the 5- or 6-membered ring formed by combining R 9 and R 1D may have a substituent.
  • the 5- or 6-membered ring substituent include an alkyl group, a substituted alkyl group, an aryl group, 0—R ⁇ —S—E :, —CO—R, —CO—O—R, and 0- CO- R, one SO - R, -S0 2 -R one NR 2, one NH- CO - R, one NH- S0 2 - R, one CO-N 2s - S0 2 - NR 2 -, one NH - CO- 0- R and single NH- CO- NR 2 is included.
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • one X to Y— is one CR 34 R 35 — CR 36 R 37 — or one C R M , R 35 , R 36 , R 37 , R 38 and R 39 are each independently a hydrogen atom, an alkyl group or an aryl group, or R 38 is bonded to R 39 To form a benzene ring or naphthalene.
  • one Z— is one 0—, one S—, one NR 40 —, —C 41 R 42 — or one CHCHCH—, and R 40 is an alkyl group or a substituted alkyl.
  • R 41 and R 42 are each independently a hydrogen atom or an alkyl group.
  • n 0 or 1.
  • R 11 and R 12 it then independently a hydrogen atom, a Al kill group or ⁇ Li Ichiru group, or: 11 and R 12 and are bonded, 5-membered ⁇ or forms a 6-membered ring.
  • benzenes h and i are optionally substituted c substituents such as halogen atom (F, Cl, Br), nitro group, cyano group, sulfo group ,
  • R is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group or an aryl group.
  • another aromatic ring or hetero ring may be condensed to the benzene rings h and i.
  • the condensed aromatic group include a benzene ring and a naphthalene ring.
  • the condensed heterocyclic ring include a furan ring, a thiophene ring, an indole ring, a pyrrol ring, a pyrazole ring, an imidazole ring and a pyridine ring.
  • examples of the polymer containing the ultraviolet-absorbing monomer represented by the general formulas (I) to (VIII) are shown, but the present invention is not limited to these specific examples.
  • the ink composition of the present invention preferably contains the polymer-fine particle dispersion in an amount of 0.1 to 0% by mass, more preferably 0.2 to 8% by mass.
  • the polymer fine particle dispersion can be prepared as a separate liquid from the ink composition, and can be applied to the image receiving material.
  • the applied amount of the solid content of the polymer-fine particle dispersion on the image receiving material is preferably from 0.1 to: LO g / m 2 , and more preferably from 0.2 to 5 g / m 2 .
  • the method for applying the polymer-fine particle dispersion of the present invention to the image receiving material is not particularly limited either. The method may be applied directly to the image receiving material, or an ink jet method may be used similarly to the ink composition. May be applied by discharging from a nozzle.
  • the order in which the ink composition and the polymer fine particle dispersion are applied on the image receiving material is not particularly limited, and the polymer fine particles are applied on the image receiving material simultaneously or after the ink composition is imagewise applied on the image receiving material.
  • the dispersion may be applied uniformly, or the ink composition may be applied imagewise after the polymer-fine particle dispersion is applied uniformly on the image receiving material.
  • the polymer-fine particle dispersion applied to the image-receiving material permeates the image-receiving material through the ink composition passing through the polymer fine-particle dispersion. It is necessary to apply the ink composition while it is in a state where it can be used.
  • a heat treatment may be performed for forming a film of the polymer fine particle dispersion.
  • the heat treatment may be performed at a temperature equal to or higher than the glass transition temperature (T g) of the polymer fine particle dispersion, and is preferably performed at about 10 ° C. higher than T g.
  • T g glass transition temperature
  • the heating means is not particularly limited, and hot air, an iron, a heated mouth nozzle, infrared rays, or the like can be used.
  • the time from application to heating is not particularly limited, but a shorter time is better. It is preferably from 1 second to 3 minutes, more preferably from 1 second to 1 minute.
  • the colorant contained in the ink composition of the present invention will be described below.
  • Hammett's substituent constant and p-value used in the following description will be described.
  • the Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, but this rule has been widely validated today. I have.
  • the substituent constants determined by Hammett's rule include the P value and the rm value, and these values can be found in many general books. For example, see JA Dean, “Lange, s Handbook”. of Chemistry, 1st and 2nd Edition, 1979 (Mc Graw-Hill) and extra edition of "The Field of Chemistry", 122, 96-: L03 page, 1979 (Nankodo) Familiar with.
  • each substituent is limited or explained by Hammett's substitution constant and p-value.
  • this is limited only to the substituent having a value known in the literature, which can be found in the above-mentioned textbook. It does not mean that it is limited, and it is needless to say that even if the value is unknown in the literature, it also includes a substituent that would fall within the range when measured based on Hammett's rule.
  • the general formula of the present invention includes a compound that is not a benzene derivative, the p-value is used as a measure of the electronic effect of the substituent regardless of the substitution position.
  • the Hammett's substituent constant is described in Japanese Patent Application Laid-Open No.
  • the colorant used in the present invention may be any of a water-soluble dye, an oil-soluble dye or a pigment.
  • water-soluble and oil-soluble dyes examples include yellow dyes, magenta dyes, and cyan dyes.
  • the yellow dye is not particularly limited and may be appropriately selected from known dyes.
  • dyes for example, phenols, naphthols, anilines, pyrazolones, pyridones, and open-chain active methylene compounds as coupling components aryl or hetarylazo dyes; for example, open-chain active methylene compounds as power coupling components
  • Azomethine dyes methine dyes such as benzylidene dyes and monomethoxonol dyes; naphthoquinone dyes;
  • quinone dyes such as quinone dyes and the like, and other dyes include quinophthalene dyes, nitro'nitroso dyes, acridine dyes, and acridinone dyes.
  • yellow dyes may exhibit a yellow color only when a part of the chromophore dissociates, in which case the count cation is an alkali metal cation or an inorganic cation such as ammonium. It may be an organic cation such as pyridinium or a quaternary ammonium salt, or a polymer cation having these in a partial structure.
  • magenta dye there is no particular limitation on the magenta dye, and it can be appropriately selected from known dyes.
  • aryl or hetarylazo dyes having phenols, naphthols, and anilines as a power coupling component
  • azomethine dyes having virazolones, pyrazo-opened triazols as a power coupling component
  • arylidene dyes And methine dyes such as styryl dyes, merocyanine dyes and oxonol dyes
  • carbonium dyes such as diphenylmethane dye, triphenylmethane dye and xanthene dye
  • quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone
  • condensed polycyclic dyes such as
  • magenta dyes may exhibit a magenta color only when a part of the chromophore dissociates, in which case the count cation is an alkali metal cation or an inorganic cation such as ammonium. It may be an organic cation such as pyridinium or a quaternary ammonium salt, or a polymer cation having these in a partial structure.
  • the cyan dye is not particularly limited and can be appropriately selected from known dyes.
  • azomethine dyes such as indoor diphosphorine dyes and indophenol dyes
  • polymethine dyes such as cyanine dyes, oxonol dyes, and merocyanine dyes
  • carbonium dyes such as diphenylmethane dye, triphenylmethane dye, and xanthene dye
  • Anthraquinone dyes for example, aryl, hetarylazo dyes having phenols, naphtholes, anilines as dye coupling components, and indigo thioindigo dyes. Cut.
  • cyan dyes may exhibit cyan only after a part of the chromophore dissociates.
  • the count cation is an inorganic cation such as alkali metal or ammonium.
  • organic cations such as pyridinium and quaternary ammonium salts, and polymer cations having these in their partial structures.
  • water-soluble dye used in the present invention include direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes. Particularly preferred are:
  • Preferred water-soluble dyes in the present invention are compounds represented by the general formula (AI).
  • AI the azo dyes represented by the general formula (A-1) of the present invention will be described in detail.
  • X 1 is an electron-withdrawing group having a Hammett's substituent constant and a p-value of 0.20 or more, preferably 0.30 to 1.0.
  • X which is an electron-absorbing I-functional group having a p-value of 0.20 or more, include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and a cyano group.
  • X 1 can further have a substituent may further have the following substituents.
  • Halogen atom for example, chlorine atom, bromine atom
  • straight or branched alkyl group having 1 to 12 carbon atoms for example, methyl, ethyl, propyl, isopropyl, t-butyl
  • aralkyl having 7 to 18 carbon atoms A group (eg, benzyl, phenethyl), an alkenyl group having 2 to 12 carbon atoms (eg, vinyl, aryl), a linear or branched alkynyl group having 2 to 12 carbon atoms (eg, ethynyl, 1-butynyl),
  • a straight-chain or branched-chain cycloalkyl group having 3 to 12 carbon atoms eg, cyclopropyl, cyclohexyl
  • a straight-chain or branched-chain cycloalkenyl group having 3 to 12 carbon atoms eg, cycloalkyl
  • Pentenyl for example, chlorine
  • phenoxycarbonylamino an imide group (for example, N-succinimide, N-furimi), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-diphenoxy_1) , 3,5-triazole-6-thio, 2-pyridylethio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenyl) Nylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), and acyl group (for example, acetyl, 3-phenylpropanoyl, penzyl) and the like.
  • an imide group for example, N-succinimide, N-furimi
  • a heterocyclic thio group for example, 2-benzothiazolylthio, 2,4-diphenoxy_1
  • Preferred examples of X 1 include a C2 to C12 acyl group, a C2 to C12 acyloxy group, a C1 to C12 dirubamoyl group, and a C2 to C12 alkyloxycarbonyl group, Carbon number?
  • aryloxycarbonyl group cyano group, nitro group, alkyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkyl group having 1 to 12 carbon atoms Sulfonyl group, arylsulfonyl group having 6 to 18 carbon atoms, sulfamoyl group having 0 to 12 carbon atoms, halogenated alkyl group having 1 to 12 carbon atoms, halogenated alkoxy group having 1 to 12 carbon atoms A halogenated alkylthio group having 1 to 12 carbon atoms, a halogenated aryloxy group having 7 to 18 carbon atoms, the number of carbon atoms substituted by two or more other electron-withdrawing groups having a crp value of 0.20 or more 7-: an aryl group of 18 and a 5- to 8-membered heterocyclic group having a nitrogen atom, an oxygen atom or an io
  • X 1 are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and most preferred is a cyano group.
  • R 51 , R 52 , R 53 , R 54 , R 55 , R 56 and Y 1 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl Kill group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amido group, arylamino group, ureido group, sulfamoylamino group, Alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterodioxy group, azo group, acryloxy group, pylbamoyloxy group, silyloxy group, Represents an ary
  • hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, alkoxy group, amide group, ureido group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group and alkoxycarbonyl group are particularly preferred. preferable.
  • Examples of the halogen atom represented by R 51 to R 56 and Y 1 include a fluorine atom, a chlorine atom and a bromine atom.
  • the alkyl group represented by R 51 to R 56 and Y 1 includes an alkyl group having a substituent and an unsubstituted alkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 12 carbon atoms.
  • the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.
  • alkyl groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl and 4-sulfobutyl.
  • the cycloalkyl group represented by R 51 to R 56 and Y 1 includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group.
  • the cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the cycloalkyl group include a cyclohexyl group.
  • the aralkyl group represented by R 51 to R 56 and Y 1 includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
  • the aralkyl group includes a carbon atom 7 or more: L 2 aralkyl group is preferred.
  • the substituent include an ionic hydrophilic group.
  • Examples of the aralkyl group include a benzyl group and a 2-phenyl group.
  • the aryl group represented by R 51 to R 56 and Y 1 includes a substituted aryl group and an unsubstituted aryl group.
  • the aryl group an aryl group having 7 to 12 carbon atoms is preferable.
  • the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group.
  • Examples of such aryl groups include phenyl, p-tolyl, p-methoxyphenyl, 0-cyclophenyl, and m- (3-sulfopropylamino) phenyl.
  • the heterocyclic groups R 56 and Y 1 represent, include heterocyclic groups and unsubstituted heterocyclic group having a substituent.
  • a 5- or 6-membered heterocyclic group is preferable.
  • the substituent include an ionic hydrophilic group.
  • the heterocyclic group include a 2-pyridyl group, a 2-thenyl group and a 2-furyl group.
  • the alkylamino group represented by R 51 to R 56 and Y 1 includes an alkylamino group having a substituent and an unsubstituted alkylamino group.
  • the alkylamino group is preferably an alkylamino group having 1 to 6 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the alkylamino group include a methylamino group and a getylamino group.
  • the alkoxy group represented by R 51 to R 56 and Y 1 includes an alkoxy group having a substituent and an unsubstituted alkoxy group.
  • the alkoxy group is preferably an alkoxy group having 1 to 12 carbon atoms.
  • the substituent include an alkoxy group, a hydroxyl group, and an ionic hydrophilic group.
  • Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, a methoxyethoxy group, a hydroxyethoxy group and a 3-carboxypropoxy group.
  • the aryloxy group represented by R 51 to R 56 and Y 1 includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
  • the aryloxy group is preferably an aryloxy group having 6 to 12 carbon atoms.
  • the substituent include an alkoxy group and an ionic hydrophilic group.
  • Said aryloxy Examples of groups include phenoxy, p-methoxyphenoxy and o-methoxyphenoxy groups.
  • the amide group represented by R 51 to R 56 and Y 1 includes an amide group having a substituent and a non-substituted amide group.
  • the amide group is preferably an amide group having 2 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the amide group include an acetoamide group, a propionamide group, a benzamide group, and a 3,5-disulfobenzamide group.
  • the arylamino group represented by R 51 to R 56 and Y 1 includes an arylamino group having a substituent and an unsubstituted arylamino group.
  • the arylamino group is preferably an arylamino group having 6 to 12 carbon atoms.
  • the substituent include a halogen atom and an ionic hydrophilic group.
  • Examples of the arylamino group include an anilino group and a 2-chloroanilino group.
  • the ureido group represented by R 51 to R 56 and Y 1 includes a substituted perido group and an unsubstituted perido group.
  • the ureido group is preferably a perido group having 1 to 12 carbon atoms.
  • the substituent include an alkyl group and an aryl group.
  • Examples of the ureido group include a 3-methylureido group, a 3,3-dimethylperido group, and a 3-phenylperido group.
  • the sulfamoylamino group represented by R 51 to R 56 and Y 1 includes a sulfamoylamino group having a substituent and an unsubstituted sulfamoylamino group.
  • substituent include an alkyl group.
  • sulfamoylamino group include N, N-dipropylsulfamoylamino.
  • the alkylthio group represented by R 51 to R 56 and Y 1 includes an alkylthio group having a substituent and an unsubstituted alkylthio group.
  • the alkylthio group is preferably an alkylthio group having 1 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the alkylthio group include a methylthio group and an ethylthio group.
  • the arylthio group represented by R 51 to R 56 and Y 1 includes an arylthio group having a substituent and an unsubstituted arylthio group.
  • the arylthio group is preferably an arylthio group having 6 to 12 carbon atoms.
  • Examples of the substituent include: And an ionic hydrophilic group.
  • Examples of the arylthio group include a phenylthio group and a p-tolylthio group.
  • the alkoxycarbonylamino group represented by R 51 to R 5S and Y 1 includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group.
  • the alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 12 carbon atoms.
  • Examples of the substituent include an ionic hydrophilic group.
  • Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.
  • the sulfonamide group represented by R 51 to R 56 and Y 1 includes a sulfonamide group having a substituent and an unsubstituted sulfonamide group.
  • the sulfonamide group is preferably a sulfonamide group having 1 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the sulfonamide group include methanesulfonamide, benzenesulfonamide, and 3-carboxybenzenesulfonamide.
  • the force-rubamoyl groups represented by R 51 to R 56 and Y 1 include a force-rubamoyl group having a substituent and an unsubstituted force-rubamoyl group.
  • the substituent include an alkyl group.
  • the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
  • the sulfamoyl group represented by R 51 to R 56 and Y 1 includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group.
  • substituent include an alkyl group.
  • the sulfamoyl group include a dimethylsulfamoyl group and a di (2-hydroxyethyl) sulfamoyl group.
  • R 51 and R 56 and the sulfonyl group represented by Y 1 include a methanesulfonyl group and a phenylsulfonyl group.
  • the alkoxycarbonyl group represented by R 51 to R 56 and Y 1 includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group.
  • the alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group. Groups.
  • the heterocyclic group represented by R 51 to R 56 and Y 1 includes a substituted heterocyclic group and an unsubstituted heterocyclic group.
  • a heterooxy group having a 5- or 6-membered hetero ring is preferable.
  • the substituent include a hydroxyl group, and an ionic hydrophilic group.
  • the heterocyclic oxy group include a 2-tetrahydrobiranyloxy group.
  • the azo groups represented by R 51 to 56 and 1 include a azo group having a substituent and an unsubstituted azo group.
  • Examples of the azo group include a ⁇ -nitrophenylazo group.
  • the acyloxy group represented by R 56 and R 1 includes a substituted alkoxy group and an unsubstituted acyloxy group.
  • the above-mentioned acyloxy group is preferably an alkoxy group having 1 to 12 carbon atoms.
  • the substituent include an ionic hydrophilic group.
  • Examples of the aforementioned acyloxy group include an acetyloxy group and a benzoyloxy group.
  • the force Rubamoiruokishi group represented by R 51 to R 5S and Upsilon 1 includes force Luba Moiruokishi group and an unsubstituted force Rubamoiruokishi group having a substituent.
  • substituent include an alkyl group.
  • carbamoyloxy group include an N-methylcarbamoyloxy group.
  • the 5 1 ⁇ R 56 and Shiriruokishi group Y 1 is represented, include Shiriruokishi group and an unsubstituted Shiriruokishi group having a substituent.
  • the substituent include an alkyl group.
  • Examples of the silyloxy group include a trimethylsilyloxy group.
  • the ⁇ reel O alkoxycarbonyl group represented by R 56 and Y 1, include ⁇ Li one Ruo alkoxycarbonyl group and an unsubstituted ⁇ reel O alkoxycarbonyl group having a substituent.
  • the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
  • R 51 ⁇ The ⁇ reel O alkoxycarbonyl ⁇ amino group R 56 and Y 1 represent, Ariruokishi force Ruponiruamino group and an unsubstituted ⁇ Li one Ruokishi force Lupo having substituent Includes nilamino groups.
  • the aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the aryloxycarbonylamino group include a phenoxylponylamino group.
  • the imido group represented by R 56 and Y 1 includes an imido group having a substituent and an unsubstituted imido group.
  • Examples of the imido group include an N-fluoroimide group and an N-succinimide group.
  • the heterodithio group represented by R 51 to R 56 and Y 1 includes a heterocyclic thio group having a substituent and an unsubstituted heterodithio group.
  • the heterocyclic thio group preferably has a 5- or 6-membered heterocyclic ring.
  • the substituent include an ionic hydrophilic group.
  • Examples of the heterocyclic thio group include a 2-pyridylthio group.
  • the sulfinyl group represented by ⁇ and Y 1 includes a substituted sulfinyl group and an unsubstituted sulfinyl group.
  • Examples of the sulfinyl group include phenylsulfinyl.
  • the phosphoryl group represented by R 56 and Y 1 includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group.
  • Examples of the phosphoryl group include a phenoxy phosphoryl group and a phenyl phosphoryl group.
  • the acyl group represented by R 51 to R 56 and Y 1 includes an acyl group having a substituent and an unsubstituted acyl group.
  • an acyl group having 1 to 12 carbon atoms is preferable.
  • the substituent include an ionic hydrophilic group.
  • the acyl group include an acetyl group and a benzoyl group.
  • the ionic hydrophilic groups represented by R 51 to R 5B and Y 1 include a carboxyl group, a sulfo group, and a quaternary ammonium group.
  • a carboxyl group and a sulfo group are preferable, and a sulfo group is particularly preferable.
  • the carboxyl group and the sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include alkali metal ions (eg, sodium ion, potassium ion) and organic cations (eg, tetramethyldanidinini). Demion).
  • each of R 51 and R 52 , R 53 and R 51 , and R 55 and R 52 form a ring May be.
  • Preferred examples of forming ⁇ are shown below.
  • A represents a group of nonmetallic atoms necessary to form a 5- to 8-membered ring (hereinafter, the ring represented by A may be referred to as “ring A”).
  • Ring A may be a saturated ring or may have an unsaturated bond.
  • the non-metal atom group is preferably a group of one or more selected from a nitrogen atom, an oxygen atom, a zeolite atom and a carbon atom, and particularly preferably only a carbon atom.
  • Examples of the ring A include a benzene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane, a cyclohexene ring, a pyridine ring, a piperazin ring, an oxane ring, and a thiane.
  • the group which may further have a substituent in the ring may be further substituted with the groups exemplified as the substituents R 51 to R 5S , Y and Z ′′ to Z 12 .
  • At least three of the nonmetallic atoms forming ring A are substituted with N atoms of the pyrazole ring, Z 11 and Z 12 , respectively, and the atoms substituted with N atoms of the pyrazole ring are Z 11 and Z 12 Flanked by both substituted atoms.
  • Ring A is preferably a benzene ring, preferably an ionic hydrophilic group at the 4-position to the N atom of the pyrazole ring in addition to the N atom of the pyrazole ring and Z 11 and Z 12 (substituted with the aforementioned substituents).
  • a benzene ring substituted with is particularly preferred.
  • Z 11 and Z 12 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, Amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfo group Famoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heteroethoxy group, azo group, acysiloxy group, rubamoyloxy group Represents a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonyl
  • a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a perido group, an alkoxycarbonylamino group, a sulfonamide group, a sulfamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an ionic hydrophilic group are particularly preferable, and a halogen atom, an alkyl group and an alkoxy group are particularly preferable, and a halogen atom is most preferable.
  • X 1 , Y, Zu , Z 12 , R 51 , R 52 , H 53 , 5 ⁇ R 55 , and R 56 represent X 1 , Y in the general formula (AI) ⁇ Zeta 11 ⁇ 12, 51 R 52, have the same meaning as R 53, R 54, RR 56 , preferably X 1, Y, Z n s Z 12, R 51, R 52, R 53, R 54, R 55 The same applies to the example of N R 56 . '
  • Z 13 , Z 14 and Z 15 each independently represent a hydrogen atom, Halogen atom, alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureide Group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterodioxy group, azo group, and acyloxy group A carbamoyloxy group, a silyloxy group, an aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocycl
  • a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, an alkoxycarbonylamino group, a sulfone amide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and Ionic hydrophilic groups are particularly preferred.
  • Z 13 , Z 14 and Z 15 include the substituents R 51 to 56 in the general formula (A-1) and the groups described above for Y 1 .
  • a hydrogen atom, a halogen atom, and an alkyl group are more preferable, and among them, a hydrogen atom is particularly preferable.
  • Z 14 includes a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a perido group, a sulfonamide group, a sulfamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an ionic hydrophilic group.
  • a hydrogen atom, an alkyl group and an ionic hydrophilic group are particularly preferable, and an ionic hydrophilic group is most preferable.
  • X 1 is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, or an arylsulfonyl group having 6 to 18 carbon atoms. And a particularly preferred one is a cyano group.
  • Y 1 is a hydrogen atom, an alkyl group, or an aryl group, and among them, a hydrogen atom is particularly preferable.
  • R 51 and Z or R 52 are an alkyl group (which may have an ionic hydrophilic group as a substituent) and an aryl group (which may have an ionic hydrophilic group as a substituent).
  • R 53 , R 54 and R 55 are hydrogen atoms and R 56 is an amide group (ionic hydrophilic May have a group as a substituent).
  • Z 11 and / or Z 12 are a halogen atom or an alkyl group.
  • Z 13 and Z 15 are a hydrogen atom, a halogen atom, or an alkyl group, among which a hydrogen atom is particularly preferred.
  • z 1 ⁇ 2 represents a hydrogen atom, a halogen atom, a sulfonamide group, a force Rubamoiru group, a sulfamoyl group, an alkoxycarbonyl group
  • Contact Yopi Ion hydrophilic group is preferably in particular Ion hydrophilic group therein.
  • a compound in which at least one of various substituents is the above-mentioned preferable group is preferable.
  • Compounds in which various substituents are the preferred groups are more preferred, and compounds in which all substituents are the preferred groups are most preferred.
  • R 51 , R 52 , R 53 , R 54 , R 56 , XYZ u , Z 12 and A and in the general formula (A-II) , R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , X 1 , YZ ", ZZZ 14 , and Z 15 represent an ionic hydrophilic group or an ionic hydrophilic group Since the azo dyes represented by the general formula (AI) and the general formula ( ⁇ - ⁇ ) have at least one ionic hydrophilic group in the molecule, they have an aqueous property.
  • the ionic hydrophilic group as a substituent of R 51 to R 56 , X 1 , Y 1 and Z U to Z 15 includes sulfo group, carboxyl group and Among these, a sulfo group and a carboxyl group are preferable, and a sulfo group is particularly preferable.
  • the carboxyl group and the sulfo group may be in the form of a salt. Examples of the counter ion forming the salt include an alkali metal ion (eg, sodium ion, potassium ion) and an organic cation (eg, tetramethylguanidinium ion). ).
  • the azo dye represented by the general formula ( ⁇ - ⁇ ) is more preferably a structure represented by the following general formula ( ⁇ - ⁇ ).
  • R 51 s R 52 and R 56 are, X 1 in the general formula (A-II), Y ⁇ Z u, ZZ 14, Each has the same meaning as R 51 , R 52 and R 56, and preferred examples are also the same.
  • substituents for the azo dye represented by the general formula (A-III) are:
  • X 1 is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfur group having 6 to 18 carbon atoms.
  • a honyl group is particularly preferable, and a cyano group is particularly preferable.
  • Y 1 is a hydrogen atom, an alkyl group, or an aryl group, and particularly a hydrogen atom.
  • R 51 and / or R 52 are an alkyl group (which may have an ionic hydrophilic group as a substituent) or an aryl group (which may have an ionic hydrophilic group as a substituent).
  • R 56 is an amide group (which may have an ionic hydrophilic group as a substituent).
  • Z 11 and Z or Z 12 are a halogen atom or an alkyl group.
  • Z 14 is a hydrogen atom, a halogen atom, a sulfonamide group, a sulfamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an ionic hydrophilic group, of which an ionic hydrophilic group is particularly preferable.
  • the preferred combination of substituents of the compound represented by the general formula (A-III) is preferably a compound in which at least one of various substituents is the above-mentioned preferred group, and more various substituents Is more preferably a compound in which all the substituents are the above-mentioned preferred groups.
  • Specific examples of the azo dyes represented by the general formulas (AI) to (A-III) (Exemplary compounds 101 to 143) are shown below.
  • the azo dyes used in the present invention are as follows. It is not limited.
  • the solubility in water of the oil-soluble dye used in the present invention is not particularly limited.
  • oil-soluble dye examples include, for example, I. Solvent Black 3, 7, 27, 29, 34;
  • Nubian Black PC-0850 Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scarlet 308, Vali Fast Blue 2606, Oil Blue BOS (Oriental Chemical Aizen Spilon Blue GNH (manufactured by Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Mazenta SE1378, Neopen Blue 808, Neopen Blue FF4012, Neopen Cyan FF4238 (manufactured by BASF), and the like.
  • a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent.
  • Preferred specific examples thereof include:
  • oil-soluble dyes include azo and azomethine dyes represented by the following formulas (B-I) and ( ⁇ - ⁇ ).
  • Dyes of the general formula (II-III) are known as dyes formed from couplers and developing agents by oxidation in photographic materials.
  • Formula (BI), the (B-II), R 61 , R 62, R 63 and R M are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic ⁇ , Shiano group , Hydroxy, nitro, amino, alkylamino, alkoxy, aryloxy, amide, arylamino, ureido, sulfamoylamino, alkylthio, aryl Luthio, alkoxycarbonylamino, sulfonamide, sulfamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocycloxy, azo, acyloxy, sulfamoyloxy, silyloxy, aryloxy Xoxycarbonyl group, aryloxycarbonylamino group, imido group, heterocyclic thio group, sulfinyl group, phosphoryl group,
  • a 1 represents —NR 65 R 66 or a hydroxy group, and R and R 66 each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
  • a 1 is preferably one NR 65 R 6S .
  • R 65 and R ss may combine with each other to form a ring.
  • H 61 and R 65 , R 63 and R 66 and / or R 61 and R 62 are bonded to each other and are aromatic ⁇ or a complex ⁇ may be formed.
  • X 2 represents a residue of a color photographic coupler, and Y 2 represents an unsaturated heterocyclic group.
  • R and R 66 are each independently preferably a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and are preferably a hydrogen atom, an alkyl group or a substituted alkyl group, an aryl group, or a substituted aryl group. It is more preferably a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or a substituted alkyl group having 1 to 18 carbon atoms.
  • R 62 is a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an amide group, a perido group, a sulfamoylamino group, an alkoxycarbonylamino group, or a sulfonamide group among the above substituents Is preferred.
  • the aliphatic group contained in the general formulas (BI) and (B-II) means an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aralkyl group and a substituted aralkyl group.
  • the aliphatic group may have a branch or may form a ring.
  • the aliphatic group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms.
  • the aralkyl portion of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, and phenyl is particularly preferred.
  • a substituted alkyl group, substituted alkenyl group, examples of the substituent for the alkyl moiety of the substituted alkynyl group and a substituted Ararukiru group include substituents cited in R 61, B s R 63 and R 64.
  • Examples of the substituent in the aryl moiety of the substituted aralkyl group are the same as the examples of the substituent in the following substituted aryl group.
  • the aromatic group contained in the general formulas (B-1) and (B-II) means an aryl group and a substituted aryl group.
  • the aryl group is preferably phenyl or naphthyl, with phenyl being particularly preferred.
  • the aryl part of the substituted aryl group is the same as the above aryl group. Examples of the substituent of the substituted aryl group include the substituents described for R 61 , 62 s R 63 and R 64 .
  • the unsaturated heterocyclic group represented by Y 2 is preferably a 5- or 6-membered unsaturated heterocyclic ring.
  • An aliphatic ring, an aromatic ring, or another heterocyclic ring may be condensed to the heterocyclic ring.
  • heteroatoms in the heterocycle include N, 0, and S.
  • Examples of the saturated heterocyclic ring include a pyrrolidine ring and a morpholine ring.
  • the sum heterocycle includes birazol, imidazole, thiazolyl, isothiazole, thiadiazol, thiophene, benzothiazole, benzoxazol, benzoisothiazol, pyrimidine, and pyridine.
  • the heterocyclic group may have the substituents described above for R 61 to R B4 .
  • the power coupler represented by X 2 in the general formula ( ⁇ - ⁇ ) is preferably the following coupler. Yellow couplers: U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, 4,248,961, JP-B-58-10739, UK Patent 1, 425,020, 1,476,760, U.S.
  • Cyan coupler U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, EP 73,636, and JP-A-4-204843 CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14 to 16), C-7, .10 (35 suitable), 34, 35 (page 37) in JP-A-4-43345, (1-1), (I-17) (pages 42 to 43), represented by the general formula (la) or (lb) in claim 1 of JP-A-6-67385. Coupler.
  • couplers described in JP-A-62-215272 page 91
  • JP-A-2-33144 pages 3, 30
  • EP355, 660A pages 4, 5, 45, 47
  • a dye represented by the following general formula (B-III) is particularly preferably used.
  • ⁇ 21 represents an electron-withdrawing group having a Hammett's substituent constant cr p value of 0.20 or more.
  • Zeta 21 is cr p value 0.3 0-1.
  • Is preferably 0 electron ⁇ I groups.
  • Preferred specific substituents include the electron-absorbing I-substituents described below. Among them, an acyl group having 2 to 12 carbon atoms, an alkyloxy group having 2 to 12 carbon atoms, a carbonyl group, and a nitro group are preferable.
  • an alkylsulfonyl group having 1 to 12 carbon atoms an arylsulfonyl group having 6 to 18 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and a halogenated alkyl group having 1 to 12 carbon atoms.
  • Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, and an arylsulfonyl group having 6 to 18 carbon atoms, and the most preferred is a cyano group.
  • R 61 to R 66 have the same meaning as in formula (B-1).
  • Z 22 represents a hydrogen atom, an aliphatic group, or an aromatic group.
  • Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
  • C is preferably a group consisting of a group of non-metallic atoms necessary to form a 5- to 8-membered ring.
  • C is an aromatic group.
  • a heterocyclic group is preferred.
  • the 5- to 8-membered group may be substituted, may be a saturated ring or may have an unsaturated bond.
  • Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a zeolite atom or a carbon atom.
  • Such a ⁇ structure ⁇ include, for example, benzene, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclohexene, pyridine, pyrimidine, pyrazine, and pyridazine. ⁇ , triazine ring, imidazo And a benzimidazole ring, an oxazolyl ring, a benzoxazolyl ring, an oxane ring, a sulfolane ring, and a thiane ring.
  • the substituent includes: The above substituent! ⁇ 1 to R 64 are exemplified.
  • the preferred dye structure represented by the general formula (B-II) is described in Japanese Patent Application No. 2000-80733.
  • the dyes represented by the general formula ( ⁇ - ⁇ ) as the magenta dye, a dye represented by the following general formula (B-IV) is particularly preferably used.
  • G is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an ester group, an amino group, a carbamoyl group, a sulfonyl group, Represents a sulfamoyl group, ureido group, urethane group, acyl group, amide group, or sulfonamide group.
  • R 61 , R 62 , AB 1 and B 2 have the same meaning as in the general formula (B- ⁇ ), and their preferred ranges are also the same.
  • C L is a ⁇ -aliphatic group, an aromatic group, a heterocyclic group, A cyano group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an ester group, an amino group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, an ureido group, a urethane group, an acyl group, an amide group, or Represents a group of atoms forming a 5- or 6-membered nitrogen-containing heterocyclic group which may be substituted with at least one sulfonamido group, and this heterocyclic group may form a condensed ring with another ring. Good.
  • L forms a 5-membered nitrogen-containing heterocyclic ring.
  • the 5-membered nitrogen-containing heterocycle include an imidazole ring, a triazole II, and a tetrazole ring.
  • magenta dye represented by the general formula (BI) or the general formula ( ⁇ - ⁇ ) will be described below, which are for describing the present invention in detail, and are described below. Is not limited.
  • magenta dye compounds described in Japanese Patent Application No. 11-365187, Japanese Patent Application No. 2001-181549, and Japanese Patent Application No. 2000-80733 can also be used, but are not limited to these.
  • the dye represented by the general formula ( ⁇ - ⁇ ) can be synthesized with reference to, for example, the methods described in Japanese Patent Application No. 2000-80733 and JP-A-55-161856.
  • the dye represented by the general formula (B-IV) can be synthesized with reference to, for example, the methods described in JP-A-4-126772, JP-B-7-94180 and JP-A-11-365187.
  • a triazo-lazomethine dye having a pyro opening represented by the following general formula (B-V) is particularly preferably used.
  • AR 61 , R 62 , B 1 and B 2 have the same meaning as the general formula (B- ⁇ ), and their preferred ranges are also the same.
  • Z 23 and Z 24 each independently have the same meaning as G in formula (B-IV).
  • Z 23 and Z M, taken together, may form a ring structure.
  • M is an atomic group capable of forming a 1,2,4-triazole ring fused to the 5-membered ring of the general formula (B-V), and two atoms B 3 and B 4 of the fused portion are one of Is a nitrogen atom and the other is a carbon atom.
  • Pirorotoriazo one Ruazomechin compound of Z 23 is Saddle Uz preparative substituent constant beauty p value represented zero. 3 0 or more of an electronic ⁇ I group is absorbed Sha one flop Is more preferable.
  • Z 23 is preferably an electron-withdrawing group having a Hammett substituent constant and a p value of 0.45 or more, and most preferably an electron-withdrawing group having a Hammett substituent constant rp value of 0.60 or more. Then, the sum of the Hammett substituent constant beauty p values of Z 23 and Z M is 0. 7 0 over those exhibits excellent hue of a cyan color, more preferred.
  • the pyrrolotriazoleazomethine compound represented by the general formula (BV) is preferably used as a cyan dye, but can be used as a magenta dye by changing the substituent.
  • Examples of electron-withdrawing groups having a Hammett substituent constant and a p-value of 0.60 or more include a cyano group, Examples thereof include a nitro group and an alkylsulfonyl group (for example, a methanesulfonyl group, an arylsulfonyl group (for example, a benzenesulfonyl group)). Hammet-substituent constant and electron-withdrawing property having a p-value of 0.45 or more.
  • Examples of the group include, in addition to the above, an acryl group (eg, an acetyl group), an alkoxycarbonyl group (eg, a dodecyloxycarbonyl group), an aryloxycarbonyl group (eg, m_chlorophenoxycarbonyl), an alkylsulfinyl group (eg, n —Propylsulfinyl), arylsulfinyl group (eg, phenylsulfinyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), halogenated alkyl group (eg, Trifluoromethyl) Hammett substituent
  • Examples of the electron-withdrawing group having a p-value of 0.30 or more include an acyloxy group (for example, acetoxy), a carpamoyl group (for example, N-eth
  • Alkoxy group for example, trifluoromethyloxy
  • halogenated aryloxy group for example, pentafluorophenyloxy
  • sulfonyloxy group for example, methylsulfonyloxy group
  • halogenated alkylthio group for example, difluoro Methylthio
  • aryl groups substituted with two or more electron-withdrawing groups having a crp value of 0.15 or more for example, 2,4-dinitrophenyl, penphenylchlorophenyl
  • complex groups for example, 2- Benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-pentimidazolyl.
  • Specific examples of the electron-absorbing I-group having a crp value of 0.20 or more include a halogen atom in addition to the above.
  • Specific examples of the cyan dye represented by the general formula (BV) used in the present invention are shown below, but these are for describing the present invention in detail, and the present invention is not limited thereto. .
  • Examples of the compound that can be used in the present invention include, but are not limited to, exemplifying compounds described in JP-A-2001-181547.
  • the pyrrolotriazo-lazomethine dyes represented by the general formula (B-V) are disclosed in JP-A-5-17979, JP-A-9-127969, JP-A-10-62992 and The compound can be synthesized with reference to the method described in Japanese Patent Application Laid-Open No. 2001-181487.
  • Examples of the pigment used in the present invention include many of inorganic pigments and organic pigments.
  • Illustrative examples of such pigments include inorganic pigments such as sulfur dominate, sulfur, selenium, zinc sulfide, cadmium sulfoselenide, graphite, zinc chromate, molybdenum red, Guinea's green, titanium white, Zinc flower, red iron oxide, chrome oxide green, lead oxide, cobalt oxide, barium titanate, titanium yellow, iron black, navy blue, lisa, cadmium red, silver sulfide, lead sulfate, barium sulfate, ultramarine, calcium carbonate , Magnesium carbonate, lead white, cobalt violet, cobalt bull, emerald green, carbon black and the like.
  • inorganic pigments such as sulfur dominate, sulfur, selenium, zinc sulfide, cadmium sulfoselenide, graphite, zinc chromate, molybdenum red, Guinea's green, titanium white, Zinc flower, red iron oxide, chrome oxide green
  • organic pigments are classified as dyes and often overlap with dyes. Specific examples include the following.
  • Yellow lake Eosin lake, Rose lake, Biored lake, Bunore lake, Green lake, Sevier lake.
  • Rhodamine lake Malachite green lake.
  • the ink composition of the present invention is prepared by dissolving and dispersing or dispersing a dye in an aqueous medium.
  • a dye in an aqueous medium.
  • an oil-soluble dye when used, it can be obtained by dispersing a high-boiling organic solvent in the form of fine particles in an aqueous medium together with the oil-soluble dye.
  • aqueous medium in the present invention refers to water or a mixture of water and a small amount of a water-miscible organic solvent to which additives such as a surfactant, a wetting agent, a stabilizer, and a preservative are added as necessary.
  • additives such as a surfactant, a wetting agent, a stabilizer, and a preservative are added as necessary.
  • the pigment When a pigment is used as the colorant, the pigment is dispersed in an aqueous medium together with a dispersant to prepare an ink composition.
  • the colorant is preferably contained in an amount of 0.2 to 20 parts by mass per 100 parts by mass of the ink composition. Further, in order to obtain a full-color image or adjust the color tone, the above-mentioned colorant may be used in combination, or another colorant may be used in combination.
  • the boiling point of the high boiling organic solvent that can be used in the present invention is preferably 150 ° C. or higher, and more preferably 170 ° C. or higher. Examples of the boiling organic solvent that can be used in the present invention include fluoric acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethyl hexyl phthalate, decyl phthalate).
  • the high-boiling point organic solvent is preferably used in an amount of 0.01 to 10 times, more preferably 0.05 to 5 times the mass of the coloring agent.
  • These high-boiling organic solvents can be used alone or in mixtures of several types (e.g. And dibutylphthalate, trioctylphosphate and di (2-ethylhexyl) sebacate, dibutylphthalate and poly (N-tert-butylacrylamide).
  • the high-boiling point organic solvent is preferably used in an amount of 0.01 to 10 times, more preferably 0.05 to 5 times the mass of the colorant.
  • the colorant and the high boiling point organic solvent are hydrophobic, they are used by emulsifying and dispersing in an aqueous medium.
  • a low boiling organic solvent may be Can be used.
  • the low boiling organic solvent is an organic solvent having a boiling point of about 30 ° C or more and 150 ° C or less at normal pressure.
  • esters eg, ethyl acetate, butyl acetate, ethyl propionate, ethoxyshethyl acetate, methyl cellosolve acetate
  • alcohols eg, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol
  • ketones eg, methylisobutylketone, methylethylketone, cyclohexanone
  • amides eg, dimethylformamide, N-methylpyrrolidone
  • ethers eg, tetrahydrofuran, dioxane
  • the like are preferably used, but are not limited thereto. It is not something.
  • Emulsification dispersion involves dispersing the oil phase, in which the dye is dissolved in a mixed solvent of a high-boiling organic solvent and, in some cases, a low-boiling organic solvent, in an aqueous phase mainly composed of water, to create fine oil droplets of the oil phase. It is done for. At this time, additives such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, a preservative, and a fungicide, which will be described later, are added to one or both of the water phase and the oil phase as needed. be able to.
  • additives such as a surfactant, a wetting agent, a dye stabilizer, an emulsion stabilizer, a preservative, and a fungicide, which will be described later, are added to one or both of the water phase and the oil phase as needed. be able to.
  • a method of emulsification a method of adding an oil phase to an aqueous phase is generally used, but a so-called phase inversion emulsification method in which an aqueous phase is dropped into an oil phase can also be preferably used.
  • fatty acid salts alkyl sulfate salts, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthylene sulfonate formalin condensates, polyoxyethylene alkyl sulfates
  • Anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxy Nonionic surfactants such as ethylene alkylamine, glycerin fatty acid ester, and oxyshylene oxypropylene block copolymer are preferred.
  • SU RFYNOLS Air Products & Chemicals
  • amoxide-type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide.
  • the surfactants listed as self-described surfactants can also be used. .
  • a water-soluble polymer can be added in combination with the above surfactant.
  • the water-soluble polymer polyvinyl alcohol, polyvinyl pyridolidone, polyethylene oxide, polyacrylic acid, polyacrylamide, and their copolymers are preferably used. It is also preferable to use natural water-soluble polymers such as polysaccharides, casein, and gelatin.
  • Polyvinyl-polyurethanes, polyesters, polyamides, polyurethanes, polycarbonates, etc. obtained by polymerization of mono-ters and acrylonitriles can also be used in combination.
  • These polymers one S 0 3 -, - it preferably contains a C 0 0-.
  • the polymer is preferably used in an amount of 20% by mass or less, more preferably 10% by mass or less of the high boiling point organic solvent.
  • an oil-soluble dye is dispersed by emulsification and dispersion to form an aqueous ink
  • a known centrifugal separation method, a microfiltration method, or the like can be used as a method for removing these coarse particles. These separation means may be performed immediately after emulsification and dispersion, or may be performed immediately after the various additives such as a wetting agent and a surfactant are added to the emulsified dispersion and then charged into the ink cartridge.
  • a mechanical emulsifying apparatus can be used as an effective means for reducing the average particle size and eliminating coarse particles.
  • emulsifying device known devices such as a simple mixer, an impeller stirring system, an in-line stirring system, a mill system such as a colloid mill, and an ultrasonic system can be used, but a high-pressure homogenizer is particularly used. It is preferred.
  • the high-pressure homogenizer is described in detail in U.S. Pat. No. 4,533,254 and Japanese Patent Application Laid-Open No. 6-47264, but as a commercially available apparatus, a go-rin homogenizer (APV GAUL IN INC.) s Microfluidizer Inc. (MI CROFLUIDEX INC.) Ultimate Inc. (Sugino Machine Co., Ltd.) and others.
  • ADV GAUL IN INC. s Microfluidizer Inc.
  • MI CROFLUIDEX INC. Microfluidizer Inc.
  • Ultimate Inc. Sugino Machine Co., Ltd.
  • a high-pressure homogenizer provided with a mechanism for forming fine particles in an ultra-high-pressure jet stream, as described in US Pat. No. 5,720,551, is particularly effective for the emulsification and dispersion of the present invention.
  • DeBEE 2000 (BEE INTERNATIONAL LTD.) Is an example of an emulsifying apparatus using this ultrahigh-pressure jet stream.
  • the pressure at the time of squeezing with a high-pressure emulsifying and dispersing apparatus is 5 OMPa or more, preferably 60 MPa or more, more preferably 18 OMPa or more.
  • emulsifiers it is particularly preferable to use two or more emulsifiers in combination, for example, by emulsifying with a stirring emulsifier and then passing through a high-pressure homogenizer. It is also preferable to once emulsify and disperse in these emulsifiers, add an additive such as a wetting agent or a surfactant, and then pass the high-pressure homogenizer again while filling the cartridge with the ink. is there.
  • an additive such as a wetting agent or a surfactant
  • a low-boiling organic solvent is contained in addition to the high-boiling organic solvent, it is preferable to remove the low-boiling solvent from the viewpoint of the stability and safety and health of the emulsion.
  • Various known methods can be used to remove the low boiling point solvent depending on the type of the solvent. That is, an evaporation method, a vacuum evaporation method, an ultrafiltration method and the like. This step of removing the low boiling organic solvent is preferably performed as soon as possible immediately after emulsification.
  • a drying inhibitor for the ink composition and the polymer fine particle dispersion of the present invention, a drying inhibitor, a penetration enhancer, an antioxidant, a viscosity modifier, a surface tension regulator, a dispersant, a dispersion stabilizer, a fungicide, Agents, pH adjusters, defoamers, chelating agents, and other additives can be appropriately selected and used in appropriate amounts.
  • a water-soluble organic solvent having a lower vapor pressure than water is preferable.
  • Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thioglycol, dithioglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, and acetylene.
  • polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol
  • polyhydric alcohols such as glycerin and diethylene glycol are more preferred.
  • the above-mentioned drying inhibitors may be used alone or in combination of two or more. These anti-drying agents are preferably contained in the ink composition and in the dispersion of Z or polymer fine particles in an amount of 10 to 5.0% by mass.
  • Examples of the penetration enhancer used in the present invention include alcohols such as ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 1,2-hexanediol, and sodium lauryl sulfate;
  • Sodium sodium oleate can be used, for example, the nonionic surfactants listed as the surfactants for dispersing in the above-mentioned formula. These have sufficient effects if they are contained in the ink composition and / or the polymer-microparticle dispersion in an amount of 10 to 30% by mass, and the range of the addition amount that does not cause printing bleeding or paper loss (print-through). It is preferable to use them.
  • the antioxidant used to improve the image storability in the present invention includes: Various organic and metal complex-based anti-fading agents can be used.
  • Organic discoloration inhibitors include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, and the like.
  • the complex includes a nickel complex, a zinc complex and the like. More specifically, Research 'Disclosure No. 17643, Paragraphs VII I through J, No. 15162, No. 18716, left column on page 650, No. 36544, page 527, No. 307105 Compounds described in the patents cited on page 872 and No. 15162 and the general formulas and typical compounds of the typical compounds described on pages 127 to 137 of JP-A-62-215272. Can be used.
  • antifungal agent used in the present invention examples include sodium dehydroacetate, sodium benzoate, sodium, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, and 1,2-benzisothiazoline 1-3. And salts thereof. These are preferably used in the ink composition and / or the polymer-fine particle dispersion in an amount of 0.02 to 1.00% by mass. The details of these are described in "Encyclopedia of Bacterial and Fungicides" (edited by the Japanese Society of Bacteria and Fungi).
  • the protective agent examples include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazol. These are preferably used in the ink composition and / or the polymer fine particle dispersion in an amount of 0.02 to 5.00% by mass.
  • Examples of the pH adjusting agent used in the present invention include hydroxides of alkali metals such as lithium hydroxide and hydrating hydroxide, carbonates such as sodium carbonate and sodium hydrogen carbonate, potassium acetate, sodium silicate, and phosphoric acid.
  • Inorganic bases such as disodium; organic bases such as N-methyldiethanolamine and triethanolamine;
  • the pH is preferably from 6 to 10, and more preferably from 7 to L0.
  • Examples of the surface tension modifier used in the present invention include nonionic, cationic and anionic surfactants.
  • fatty acid salts as anionic surfactants Alkyl sulfates, alkyl benzene sulfonates, alkyl naphthylene sulphonates, dialkyl sulfosuccinates, alkyl phosphates, naphthylene sulfonic acid formalin condensates, polyoxyethylene alkyl sulfates, etc.
  • nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene S fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene alkyla. And glycerin fatty acid ester, oxishylene oxypropylene block copolymer and the like.
  • SURFY NOLS Air Products & Chemicals
  • amine oxide type amphoteric surfactants such as N, N-dimethyl_N-alkylamine oxide are preferable.
  • the surfactants described in JP-A-59-157,636, pages (37)-(38), Research 'Disclosure No. 308119 (1989) can also be used.
  • the surfactant used here preferably has a solubility in water at 25 ° C of 0.5% or more.
  • the surface tension of the ink composition and the dispersion of Z or polymer-fine particles of the present invention is preferably 20 to 6 OmN / m with or without these. Further, it is preferably from 25 to 45 mN / m.
  • the viscosity of the ink composition and the dispersion of Z or polymer-fine particles of the present invention is preferably 30 mPa ⁇ s or less. Further, since it is more preferable to adjust the viscosity to 2 OmPa ⁇ s or less, a viscosity modifier may be used for the purpose of adjusting the viscosity. Examples of the viscosity modifier include water-soluble polymers such as celluloses and polyvinyl alcohol, and nonionic surfactants.
  • the above-mentioned various cation, anion, and nonionic surfactants as a dispersant and a dispersion stabilizer, and a chelating agent represented by a fluorine-based, a silicone-based compound, and EDTA as an antifoaming agent are also required.
  • a known recording material that is, a plain paper, a resin-coated paper, for example, Japanese Patent Application Laid-Open No.
  • the support for recording paper and recording film consists of chemical pulp such as LBKP S NB KP, mechanical pulp such as GPP GW, MPs T MPs CT MP, CMP, CGP, waste paper pulp such as DIP, etc.
  • Additives such as conventionally known pigments, binders, binders, sizing agents, fixing agents, cationic agents, and paper strength enhancers are mixed, and those manufactured by various equipment such as Fourdrinier paper machines and circular web paper machines are used. It is possible.
  • any of synthetic paper and plastic film sheet may be used.
  • the support preferably has a thickness of 10 to 250 ⁇ m and a basis weight of 10 to 25 Og / m 2. .
  • the support may be provided with an image receiving layer and a back coat layer as they are, or after providing a size press or an anchor coat layer with starch, polyvinyl alcohol, or the like, and then providing an image receiving layer and a back coat layer. Further, the support may be subjected to a flattening process using a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
  • a calendar device such as a machine calendar, a TG calendar, or a soft calendar.
  • paper and plastic film laminated on both sides with polyolefin eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
  • polyolefin eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof
  • a white pigment eg, titanium oxide, zinc oxide
  • a coloring dye eg, cobalt pull, ultramarine, neodymium oxide
  • the image receiving layer provided on the support contains a pigment and an aqueous binder.
  • a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, silver, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, anoremina, lithbon,
  • examples include inorganic white pigments such as zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide, and zinc carbonate; and organic pigments such as styrene-based pigments, acrylic pigments, urea resins, and melamine resins.
  • a porous inorganic pigment is preferred, and in particular, synthetic amorphous silica having a large pore area is suitable.
  • synthetic amorphous silicon any of silicic anhydride obtained by a dry production method and hydrous silicic acid obtained by a wet production method can be used, but it is particularly preferable to use hydrous silicic acid. Two or more of these pigments may be used in combination.
  • aqueous binder contained in the image receiving layer examples include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylyloliolidone, polyalkylene oxide, and polyalkylene oxide.
  • examples thereof include water-soluble polymers such as alkylene oxide derivatives, and water-dispersible polymers such as styrene butadiene latex and acryl emulsion.
  • These aqueous binders can be used alone or in combination of two or more.
  • polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and peel resistance of the ink receiving layer.
  • the image receiving layer may contain a mordant, a water-proofing agent, a light-fastness improver, a surfactant, a hardener, and other additives in addition to the pigment and the aqueous binder (aqueous binder).
  • the mordant added to the image receiving layer is preferably immobilized.
  • a polymer mordant is preferably used.
  • An image receiving material containing a polymer mordant described on pages 212 to 215 of JP-A-1-161236 is particularly preferred.
  • the use of the polymer mordant described in the publication makes it possible to obtain an image with excellent image quality and to improve the light fastness of the image.
  • the waterproofing agent is effective for making the image waterproof, and as such a waterproofing agent, a thiothion resin is particularly desirable.
  • a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiarylammonium chloride polymer, cationic polyacrylamide, and colloidal silica.
  • the polyamide polyamine epichlorohydrin is particularly preferred.
  • the content of these cationic resins is preferably from 1 to 15% by mass, and more preferably from 3 to 10% by mass, based on the total solid content of the ink receiving layer.
  • the light resistance improver examples include zinc sulfate, zinc oxide, hindered amine-based antioxidant, benzophenone-based and benzotriazole-based ultraviolet absorbers. Of these, zinc sulfate is particularly preferred.
  • Surfactants function as coating aids, release improvers, slipperiness improvers, or antistatic agents.
  • the surfactants are described in JP-A Nos. 62-173463 and 62-183457.
  • organic fluoro compound may be used in place of the surfactant.
  • the organic fluoro compound is preferably ⁇ -soluble.
  • examples of organic fluoro compounds include fluorinated surfactants, oily fluorinated compounds (eg, fluorinated oils), and solid fluorinated resin resins (eg, tetrafluoroethylene resin).
  • the organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994 and JP-A-62-135826.
  • Materials described on page 222 of JP-A-11-161236 can be used as the hardener.
  • Other additives to be added to the image receiving layer include pigment dispersants, thickeners, defoamers, dyes, fluorescent brighteners, preservatives, pH adjusters, matting agents, hardeners, and the like. .
  • the number of image receiving layers may be one or two.
  • a recording paper and a recording film may be provided with a back coat layer. Examples of components that can be added to this layer include a white pigment, an aqueous binder (a seven-color binder), and other components.
  • white pigments contained in the back coat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate.
  • Diatomaceous earth calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudo-mite, hydroxylated aluminum aluminum, alumina, lithopone, zeolite, hydrohalosite, magnesium carbonate, hydroxyl Organic pigments such as white inorganic pigments such as magnesium oxide, styrene-based plastic pigment, acryl-based plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin.
  • white inorganic pigments such as magnesium oxide, styrene-based plastic pigment, acryl-based plastic pigment, polyethylene, microcapsules, urea resin, and melamine resin.
  • the aqueous binder contained in the back coat layer includes styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, and silanol.
  • Water-soluble polymers such as styrene-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylidene, and water-dispersible polymers such as styrene-butadiene latex and acrylic emulsion And the like.
  • a polymer fine particle dispersion may be added to the constituent layers (including the back layer) of the recording paper and the recording film.
  • the polymer fine particle dispersion is used for the purpose of improving film properties such as dimensional stability, curling prevention, adhesion prevention, and film crack prevention.
  • the polymer fine particle dispersion is described in Japanese Patent Publications Nos. 624-245258, 623-136664, and 621-110666. is there.
  • Example 1 the present invention will be described with reference to Examples, but the present invention is not limited thereto.
  • Example 1 the present invention will be described with reference to Examples, but the present invention is not limited thereto.
  • the polymer fine particle dispersion of the following components was obtained by adding 20% by mass of an ultraviolet absorbing polymer (I_pl) to the polymer fine particle dispersion (P-1) in the specification.
  • ink sets 102 to 109 were prepared in the same manner as the ink set 101 except that the polymer fine particle dispersion and the ultraviolet absorbing polymer were changed as shown in Table 5.
  • the polymer-fine particle dispersion was added so that the solid content was 5% by mass with respect to the ink composition.
  • a comparative ink set 109 was prepared according to the same formulation as the ink set 101 except that the polymer fine particle dispersion was not contained.
  • these ink sets 101 to 109 are packed into the ink jet pudding Yuichi PM 770C cartridge manufactured by EPSON, and the same machine is used to print images on Fuji Photo Film Ingejet Paper Photo Glossy Paper EX. Was printed.
  • Light fastness is measured by measuring the image density Ci immediately after printing with an X-rite 310, and then applying xenon light (85,000 looks) to the image using an Atlas Weatherme One Night. After irradiation for 20 days, the image density Cf was measured again, and the residual dye ratio Cf / Ci * 100 was determined and evaluated. Evaluate the residual dye rate at three points of reflection density of 1, 1.5, and 2.A: When the residual dye rate is 70% or more at any concentration, A: C when the concentration was less than 70% at all concentrations.
  • the concentration before and after storing the sample for 10 days under the condition of 80 ° C. was measured with X-rite 310 to obtain and evaluate the residual dye ratio.
  • the reflection density was evaluated at three points of reflection density of 1, 1.5, and 2.A: When the dye retention rate was 90% or more at any concentration, A: When the two points were less than 90%: B, 9 at all concentrations
  • the coarse particle dispersion was passed five times with a pressure of 6 OMpa using a micro-mouth dicer (MI CROFLUIDEX INC) to perform fine particle filtration. Furthermore, the solvent was removed from the resulting emulsion at a rotary evaporator until the odor of ethyl acetate disappeared.
  • MI CROFLUIDEX INC micro-mouth dicer
  • the dispersion of polymer fine particles (P-1) is added to the ultraviolet absorbing polymer.
  • the polymer dispersion was added so that the solid content was 5% by mass of the ink composition.
  • the volume average particle size of the obtained emulsified dispersion ink was measured using a Microtrac UPA (manufactured by Nikkiso Co., Ltd.) and found to be 5 lnm.
  • Table 7 shows the composition of the final composition after solvent evaporation.
  • ink sets 202 to 209 were prepared in the same manner as the ink set 201 except that the polymer fine particle dispersion and the ultraviolet absorbing polymer were changed.
  • the polymer-fine particle dispersion was added so that the solid content was 5% by mass with respect to the ink composition.
  • a comparative example ink set 209 was prepared with the same formulation as the ink set 201 except that the polymer fine particle dispersion was not contained.
  • these ink sets 201 to 209 were packed in EPSON Inkjet Print Yuichi PM770C power cartridges, and the same machine was used to print images on Fuji Photo Film Inkjet Paper Photo Glossy Paper EX. Printed.
  • Deionized water was added to the following components to make 1 liter, and the mixture was stirred for 1 hour while heating at 3040 ° C. Thereafter, the pH was adjusted to 9 with K0H1 Omo1 / 1, and the mixture was filtered under reduced pressure through a microfil having an average pore diameter of 0.25 ⁇ m to prepare a light magenta ink.
  • the sample was ejected and applied so that the applied amount of the solid content was 0.5 gZm 2 on the image to prepare Sample 301.
  • samples 302 to 109 were prepared in the same manner as sample 301 except that the types of the polymer fine particle dispersion and the ultraviolet absorbing polymer were changed.
  • the amount of the ultraviolet absorbing polymer added was 20% by mass based on the original polymer-fine particle dispersion.
  • two or more types of polymer fine particle dispersions were used, they were used in equal amounts so that the total coating amount was 0.5 g / m 2 in solid content.
  • the UV-absorbing polymer (I-P1) was added to the polymer-particle dispersion P_1 and diluted with deionized water to a solid content of 5% by mass.
  • the dispersion was uniformly coated so that the applied amount of the solid content of the polymer-microparticle dispersion was 0.5 g / m 2, and immediately thereafter, an image was printed using Ink Set A to prepare Sample 401.
  • Samples 402 to 409 were prepared in the same manner as Sample 401 except that the types of the polymer fine particle dispersion and the UV-absorbing polymer were changed as shown in Table 13.
  • the coarse particle dispersion was passed five times with a pressure of 6 OMpa with a micro-mouth dicer (MI CROFLUIDEX INC) to perform fine particle filtration. Further, the resulting emulsion was desolvated in a low-evaporation evaporator until the odor of ethyl acetate disappeared.
  • Table 15 shows the composition of the final composition after solvent evaporation.
  • an image was printed on an inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. using an inkjet printer PM-1770C (ink set B) manufactured by EPSON.
  • an ultraviolet absorbing polymer I_p1
  • P-1 polymer fine particle dispersion particle size: 0.2 ⁇ m
  • a liquid diluted with deionized water was ejected in an ink jet printer at night, and the solid content was applied on the image so as to have a coating amount of 0.5 g / m 2 , thereby preparing a sample 501.
  • the UV-absorbing polymer (I-p1) was added to the polymer-particle dispersion P-1 and diluted with deionized water to a solid content of 5% by mass. 0.5 g / m of solid content of polymer fine particle dispersion
  • the present invention can provide an image having excellent light fastness (light fastness), heat fastness (weather fastness), and water fastness. Industrial applicability
  • the present invention can be used for an inkjet recording method without any particular limitation.
  • the present invention relates to a known method, for example, a charge control method for discharging ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) using oscillating pressure of a piezo element, and an electric signal as an acoustic beam. It is used in the acoustic ink jet method that irradiates the changed ink and discharges the ink using radiation pressure, and the thermal ink jet (bubble jet) method that heats the ink to form bubbles and uses the generated pressure. .
  • Inkjet recording methods include a method of ejecting a large number of low-density inks called photo inks in small volumes, a method of improving image quality by using multiple inks with substantially the same hue and different densities, and a method of colorless and transparent.
  • the present invention is used for any of these methods.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Ink Jet (AREA)

Abstract

L'invention concerne une composition d'encre contenant une dispersion de fines particules polymères renfermant un polymère dont sa structure partielle possède un composé spécifique capable d'absorption ultraviolets. L'invention concerne également un procédé d'enregistrement d'image à jet d'encre utilisant la dispersion de fines particules polymères au moment de l'enregistrement. On peut améliorer la capacité de mémorisation d'images enregistrées en formant un fil de revêtement sur les images.
PCT/JP2003/001715 2002-02-20 2003-02-18 Composition d'encre et procede d'enregistrement d'image a jet d'encre WO2003070841A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2002-043684 2002-02-20
JP2002-043683 2002-02-20
JP2002043684 2002-02-20
JP2002043683 2002-02-20

Publications (1)

Publication Number Publication Date
WO2003070841A1 true WO2003070841A1 (fr) 2003-08-28

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08183242A (ja) * 1994-12-28 1996-07-16 Mitsubishi Paper Mills Ltd インクジェット記録シート
JPH10279854A (ja) * 1997-04-07 1998-10-20 Seiko Epson Corp 耐光性に優れた画像を実現するインク組成物
JPH1112519A (ja) * 1997-04-28 1999-01-19 Seiko Epson Corp 耐光性に優れた画像を実現するインク組成物
JP2001138625A (ja) * 1999-11-15 2001-05-22 Mitsubishi Chemicals Corp インクジェット記録シート
JP2001226615A (ja) * 2000-02-18 2001-08-21 Fuji Xerox Co Ltd インクジェット記録用インクセットおよびインクジェット記録方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08183242A (ja) * 1994-12-28 1996-07-16 Mitsubishi Paper Mills Ltd インクジェット記録シート
JPH10279854A (ja) * 1997-04-07 1998-10-20 Seiko Epson Corp 耐光性に優れた画像を実現するインク組成物
JPH1112519A (ja) * 1997-04-28 1999-01-19 Seiko Epson Corp 耐光性に優れた画像を実現するインク組成物
JP2001138625A (ja) * 1999-11-15 2001-05-22 Mitsubishi Chemicals Corp インクジェット記録シート
JP2001226615A (ja) * 2000-02-18 2001-08-21 Fuji Xerox Co Ltd インクジェット記録用インクセットおよびインクジェット記録方法

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