WO2003070841A1 - Ink composition and method of ink jet image recording - Google Patents

Abstract

An ink composition comprising a polymer fine-particle dispersion containing a polymer having in its partial structure a specified compound capable of ultraviolet absorption. A method of ink jet image recording wherein the polymer fine-particle dispersion is used at the time of recording. The storability of recorded images can be enhanced by forming a coating film on the images.

Description

 Description Ink composition, jet image recording method

 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. In particular, 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. Background art

 In recent years, with the spread of computers, ink jet pudding has been widely used not only in offices but also at home for printing on paper, film, cloth, etc. 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.

(Fused type) Inks are used, and water-based inks are the mainstream in terms of manufacturing, handling, odor and safety.

 Colorants used in ink compositions containing these ink jet recording inks

(Dyes and pigments) High solubility in solvents, High density recording possible, Good hue, Excellent fastness to light, heat, air, water and chemicals It is required to have good fixability to the image receiving material, to be difficult to see, to have good storage stability as ink, to be non-toxic, to have high purity, and to be available at low cost. . However, it is extremely difficult to search for a colorant that meets these requirements at a high level. Although various dyes and pigments have been proposed and used in practice, no colorant that satisfies all requirements has yet been found.

 With well-known dyes and pigments, such as color index (C.I.) numbers, it is difficult to achieve both the hue and robustness required for ink-jet recording inks. .

 As a dye for improving the fastness, an azo dye derived from an aromatic amide and a 5-membered complex amide described in Japanese Patent Application Laid-Open No. 55-166568 is proposed. However, these dyes have unfavorable hues in the yellow and cyan regions, and thus have a problem of deteriorating color reproducibility. 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. However, the dyes used in each publication have insufficient improvement in hue, and when used as a water-soluble ink, have insufficient solubility in water. In addition, when the dyes described in each of the publications are used as water-soluble inks for ink jet, there is a problem in fastness to wet heat. As a means for solving these problems, 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. However, it was found that 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.In addition to the degradation reaction due to heat, 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.

 In addition, many water-based inks use water-soluble dyes that dissolve in the molecular state, so they have the advantage of high transparency and high color density, but have poor water resistance and cause bleeding when printed on so-called plain paper. This has the disadvantage that the printing quality is significantly reduced and the weather resistance is extremely poor. In recent years, it has been known that gases such as ozone are affected in terms of weather resistance.

In order to improve the image storability such as the above-mentioned water resistance, weather resistance, light resistance, etc., 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.

 On the other hand, a method of forming a film on the image surface to block the contact between the colorant and water, oxygen, ozone, NOx, etc., and to improve the robustness is being studied.

 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. In this method, 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.

 In Japanese Patent Application Laid-Open Nos. 7-237348 and 8-29090, 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.

 Although a method of laminating a transparent film on the image surface (Japanese Patent Publication No. 113-133419) has also been performed, it is difficult to use a film that is too thin in the operation of laminating, and therefore, it is difficult to use it. There is a problem that the thickness of the obtained image is increased.

Instead of the laminating method, there is also a method of applying and curing a thermosetting resin coating or a radiation hardening resin coating on an image surface (Japanese Patent Laid-Open No. 7-188595). In these methods, 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

 Accordingly, 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.).

 The above object is achieved by the following ink composition and ink jet image recording method.

 1. An ink composition containing a colorant and a polymer fine particle dispersion, wherein the polymer fine particle dispersion has at least one selected from the group of compounds represented by the following general formulas (I) to (VIII) as a partial structure: An ink composition characterized by containing a polymer having the same. General formula (I)

式中、 璟 aおよび bは、 置換基を有していてもよい

In the formula, 璟 a and b may have a substituent

 -General formula (II

In the formula, Ar ¹ is an aryl group or an aromatic heterocyclic group; -L 1 is a single bond or 10-; and the benzene ring c may have a substituent.

General formula

In the formula, the benzene ring d and the triazine 璟 e may have a substituent; Another aromatic ring or hetero ring may be condensed to the benzene ring d.

General formula (IV

 In the formula, the benzene rings f and g may have a substituent.

General formula (V)

R ¹ R ²

 \ /

 C = C

Ar ² R ³

Wherein 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. General formula (VI) / ^R6

 N— CH = CH— CH2 C

In R ⁷ Formula, 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)

: CH— CH:

During ^chi ～Nyu R 10 formula, R ⁸ is an alkyl group, a substituted alkyl group or Ariru group; R ⁹ and R ¹⁰ are then it independently, Shiano group, one COR ^27, One COOR ^28, - CONR ²⁹ Ε—S0 ₂ R ³¹ or —S 0 ₂ NR ³² R ³³ , wherein R ^{27 to} R ³³ are each independently a hydrogen atom, an alkyl group, a substituted alkyl group or an aryl group, or R ⁹ and R ^w combine to form a 5-membered ring or 6-membered ring; -X to Y— is -CR ³⁴ R ³⁵ —CR ³⁶ R ³⁷ — or _CR ³⁸ = CR ³⁹ — R ³⁴ -R ³⁹ are each independently a hydrogen atom, an alkyl group or an aryl group, or R ³⁸ and R ³⁹ combine to form a benzene ring or a naphthylene ring One Z— is one 0—, one S one, one NR ⁴⁰ —, one CR ⁴¹ R ⁴² — or one CH = CH—, where: R ⁴⁰ is an alkyl group, a substituted alkyl group or Re A le radical, R "and R ^42, it it independent, is hydrogen or an alkyl group; n is 0 or 1.

General formula (VIII)

In the formula, 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. And benzene rings h and i may have a substituent; a benzene ring]! And i may be condensed with another aromatic ring or heterocyclic ring.

 2. The ink composition according to the above 1, wherein the ink composition contains 0.1 to 10% by mass of a polymer fine particle dispersion.

 3. 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.

4. Simultaneously with or after discharging the ink composition containing the colorant onto the image receiving material to form an image, a solution containing the polymer-microparticle dispersion is applied to the image receiving material. An inkjet image recording method, wherein the polymer fine particle dispersion is as described above.

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.

 5. 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.

6. The inkjet image recording method according to the above item 4 or 5, wherein the applied amount of the polymer-fine particle dispersion is 0.1 to 10 g / m ^{2 in} terms of solid content.

 7. The ink jet image recording method according to any one of the above items 3 to 5, wherein the image receiving material has an image receiving layer containing a white inorganic pigment. That is, 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.

 Since 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.

When recording an image, 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. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail.

 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. There is no particular limitation on the 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

 (a) 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.

 (b) a,? -unsaturated carboxylic acids and salts thereof: acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, potassium itaconate and the like.

(c),? —Derivatives of unsaturated carboxylic acids: 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 acrylate, tetrahydrofurfuryl methacrylate, 2-Metokishechirume evening acrylate, .omega.-methoxy polyethylene glycol menu evening chestnut Rate (molar number of polyoxyethylene added = 2 to 100), polyethylene glycol monomethacrylate (molar number of added polyoxyethylene = 2 to 100), polypropylene glycol monomethacrylate ( Number of moles of polyoxypropylene added = 2 to 100), 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfoptyl methacrylate, 3-trimethoxy Derivatives of unsaturated dicarboxylic acids (eg, monobutyl maleate, dimethyl methyl maleate, monomethyl itaconate, dibutyl itaconate), polyfunctional esters

(For example, 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,

1, 2, 4-cyclohexanetrimethacrylate, etc.).

 (d) 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.

(e) 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. (f) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxethyl vinyl ether and the like.

 (g) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, and vinyl acetate.

 (h) Other polymerizable monomers: N-vinylpyrrolidone, 2-vinyloxazoline, 2-isopropynyloxazoline, divinylsulfone, and the like.

 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. Among these, 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. 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentene, 1-phenyl-1,3-butadiene, 1-naphthyl-1,3-butadiene, 1 —? —Naphthyl 1,3-butadiene, 2-chloro_1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichlor 1,3-butadiene, 1,1,2-trichloro-1,3-butadiene and 2-cyano-1,3-butadiene, 1,4-hexadiene, cyclopentenegen, ethylidene norbornene, etc. Can be mentioned. Table 1 below shows specific examples of the polymer preferably selected in the polymer-fine particle dispersion of the present invention, but the present invention is not limited thereto. Specially here Unless otherwise stated, the numerical value indicating the composition ratio of each monomer indicates a mass percentage.

 table 1

これらのポリマー微粒子分散物は単独で用いてもよいし、 必要に応じて 2種以 上を併用してもよい。 本発明のポリマー微粒子分散物を合成するために用いられる乳化重合法につい て以下に説明する。

These 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.).

Replacement form (Rule 26) About 5 to 150% by weight of the monomer based on the dispersion medium is emulsified with 0.1 to 20% by weight of the monomer based on the emulsifier, and 0.02 to 5% by weight of the monomer based on radical polymerization The reaction is generally carried out with stirring at a temperature of 30 ° C. to about 100 ° C., preferably 40 ° C. to 90 ° C. The amount of the organic solvent miscible with water is from 0 to 100%, preferably from 0 to 50%, by volume relative to water.

 Examples of the polymerization initiator include azobis compounds, peroxides, phenols, hydroxides, and redox catalysts, such as potassium persulfate and ammonium persulfate.

Replacement form (Rule 26) 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.

 In emulsion polymerization, it goes without saying that the polymerization initiator, concentration, polymerization temperature, reaction time, and the like can be widely and easily changed according to the purpose. Also, ? 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 (）)) ".

As 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. Examples of the polymer containing a dissociating group 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, 2-methylacrylamido-2-methylpropanesulfonic acid) and the like. Examples of the monomer containing phosphoric acid as a dissociating group include monoacryloyloxyshethyl phosphate and monomethacryloyloxyshethyl phosphate.

 Of these, 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.

 Further, 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-methoxybutyl acrylate, 2-ethoxyhexyl acrylate, 2-butoxyshetyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, glycidyl acrylate, 1 —Promo 2-Methoxyethyl acrylate, 2,2,2—Trifluoroethyl acrylate, 1 H, 1 H, 2 H, 2 H-Perfluorodecyl acrylate, diphenyl 2-diacryloyloxethyl phosphite, diphenyl 2-methyl chloroyloxyshethyl phosphate, dibutyl 2- Acryloyloxyethyl phosphate and the like.

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, 3-Methoxybutylmethacrylate, 2-Ethoxymethacrylate, 2-butoxyshethylmethacrylate, 2- (2-methoxyethoxy) ethylmethacrylate, 2- (2-ethoxy) Ethoxy) ethyl methacrylate, 2-acetoxethyl methacrylate, 2-acetoacetoxethyl acrylate, aryl acrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 1H, 1 H, 2 H, 2 H—Perfluorodecyl methacrylate, Gio Cutyl-2-methacryloyloxyshetyl phosphate and the like.

 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,

1-butene, 1-pentene, vinyl chloride, vinyl chloride vinyl chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, etc., styrenes, for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene Examples include len, chloromethylstyrene, methoxystyrene, acetostyrene, chlorostyrene, dichlorostyrene, bromostyrene, and methyl vinyl benzoate.

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.

 It is also preferable to copolymerize 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. Of 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.

 Next, the above-mentioned condensation group-containing condensation polymer will be described in detail.

 The polyurethane containing a dissociating group is basically synthesized by a polyaddition reaction using a diol compound and a diisocyanate compound as raw materials.

Specific examples of the diol compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,3-butanediol, and non-dissociable diols. 2,2-Dimethyl-1,3-propanediol, 1,4-pentyldiol, 2,4-pentyldiol, 3,3-dimethyl-1,2-butanediol, 2-ethyl-2-methyl 1,3-propanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentynediol, 2,2-getyl-1,3-propanediol, 2,4 1-dimethyl-2,4-pentenediol, 2-methyl-1-propyl-1-1,3- Propanediol, 2,5-dimethyl-1,2,5-hexanediol, 2-ethizole-1,3-hexanediol, 1,2-octanediol, 2,2,4-trimethyl-1,3-phenylene Diol, 1,4-cyclohexane dimethanol, ethylene glycol, triethylene glycol, dipropylene glycol, propylene glycol, polyethylene glycol (average molecular weight = 200 to 4000), polypropylene glycol (average molecular weight = 200 to 1000) , Polyesterpolyol, 4,4, dihydroxydiphenyl-1,2,2-propane, 4,4'-dihydroxyphenylsulfone and the like.

 Preferred specific examples of the diisocyanate 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. Examples of diols having a dissociating group, particularly an anionic group, 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. However, 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.

 Specific examples of 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, ω-poly (ethylene oxide) dicarboxylic acid, ρ-xylylenedicarboxylic acid, etc. Can be mentioned.

 These compounds may be used in the form of an alkyl ester of dicarboxylic acid (eg, dimethyl ester) 酸 塩 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, -Ο Ρ (Ο Η) ₂ , sulfinic acid groups, or salts thereof (for example, alkali metal salts such as Νa 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. Can be 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.

 As the 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. And 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.

 Examples of diamine dani include ethylenediamine, 1,3-propanediamine, 1,2-propanediamine, hexamethylenediamine, octamethylenediamine, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. 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, ω-aminohexanoic acid, ω-aminodecanoic acid, ω-aminoundecanoic acid, and anthranilic acid. In addition, examples of monomers that can be used in ring-opening polymerization include: one-strand prolactam, azetidinone, and pyrrolidone.

 As the 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. Further, after the polymerization of each 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.

 For the above-mentioned polymer containing a dissociating group, 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). And the solubility, compatibility with the dye, and stability of the dispersion) can be used in any proportion.

 Further, among the polymers containing a dissociating group, 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.

In addition, 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. In amines, organic acids (eg, acetic acid, Salts of propionic acid, methanesulfonic acid) and inorganic acids (such as hydrochloric acid and sulfuric acid) may be used.

 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.

Specific examples of the vinyl group-containing vinyl polymer are listed in Table 2 below. The ratio in parentheses means the mass ratio. Note that the present invention is not limited to these specific examples.

Table 2

差替え用紙 （規則 26) PP-30)ェチルァクリレート- tert-ブチルメタクリレート- 2-アクリルアミド- 2-メチルプロパンスル ホン酸共重合体 (35:60:5)

Replacement form (Rule 26) PP-30) Ethyl acrylate-tert-butyl methacrylate-2-acrylamide-2-methylpropanesulfonic acid copolymer (35: 60: 5)

 PP-31) Tert-butyl acrylate-tetrahydrofurfuryl acrylate- 2-methylpropanesulfonate copolymer (50:40:10)

 PP-32) Methacrylic acid ester of tert-butyl acrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeating number 23) -2-acrylamide-2-methylpropanesulfonate (70: 27: 3)

 PP-33) Isobutyl acrylate-N-vinylpyrrolidone-2-acrylamide-2-methylpropanesulfonic acid copolymer (65: 30: 5)

 PP-34) Isobutyl methacrylate-2-acrylamide-2-sodium methylpropanesulfonate copolymer (88:12)

 PP-35) n-butyl acrylate-tert-butyl methacrylate-vinyl sulfonic acid copolymer (30:60:10)

 PP-36) Ethyl acrylate-tert-butyl methacrylate-vinyl sulfonic acid copolymer (60:30:10)

PP-37) Ethyl methacrylate-2-acrylamide-2-methylbutanesulfonic acid copolymer (90:10)

Specific examples of the 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

Replacement form (Rule 26) —

 26 All WW groups are shown in non-dissociated form. Regarding those produced by condensation reaction, such as polyester and polyamide, the constituent components are all represented by dicarboxylic acids, diols, diamines, hydroxycarboxylic acids, aminocarboxylic acids and the like, regardless of the raw materials. The ratio in parentheses means the molar percentage ratio of each component.

 Table 3

Replacement form (Rule 26) PP-52) Reaction product of poly (12-aminododecanoic acid) and maleic anhydride (100)

 (PP-53) 11-aminoundecanoic acid 7-aminoheptanoic acid (50/50)

 PP-54) Hexamethylenediaminenoadipate (50/50)

 PP-55) N, N-dimethylethylenediamine adipic acid cyclohexanedicarponic acid (50/20/30)

PP-56) hexamethylenediamine 2 toluene di iso Xia sulfonate Z, 2 - bis (hydroxymethyl) propionic acid ⁽⁵ 0/40/10)

 PP-57) 11-aminoundecanoic acid hexamethylene diamine nourea (34/33/33)

Regarding the synthesis of the condensation polymer containing a dissociating group, see “Polymer Experimental Studies (Vol. 5) Polycondensation and Polyaddition (Edited by Shu Kamihara, published by Kyoritsu Shuppan Co., Ltd. (1980))”, “Polyester Resin Handbook” (Eiichiro Takiyama, published by Nikkan Kogyo Shimbun (1988))

Replacement form (Rule 26) Resin Handpuck (edited by Keiji Iwata, published by Nikkan Kogyo Shimbun (1987)) j, "Experimental Method for Polymer Synthesis (by Takayuki Otsu and Masayoshi Kinoshita, published by Kagaku Doujinshi (1972))", Tokusho Sho 331-1114 Nos. 37-7641, 39-5989, 40-27349, 42-5118, 42-24194, 45-10957, 48-25435, 49-36942 And publicly known methods described in JP-A-56-88454, JP-A-56-88454, and JP-A-6-340835. 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.

General formula (I)

一般式 （I) 中、 ベンゼン璟 aおよび bは、 置換基を有していてもよい。 置換 基の例には、 ハロゲン原子 （F、 Cl、 Br)、 ニトロ基、 シァノ基、 スルホ基、 アルキル基、 置換アルキル基、 アルケニル基、 置換アルケニル基、 ァリール基、 複素環基、 — 0 - R、 一 S - R、 一 CO - R、 一 CO - 0 - R、 一 0— CO— R、 一 SO -： R、 一 S0₂ - R、 一 NR₂、 一 NH— CO - R、 一題— S0₂ - R、 一 CO— NR₂、 一 S0₂— NR₂—、 一 NH— CO— 0— Rおよび一 NH— CO— N R₂が含まれる。 上記 Rは、 水素原子、 アルキル基、 置換アルキル基、 アルケニ ル基、 置換アルケニル基またはァリール基である。 本発明の紫外線吸収性モノマーに含まれるアルキル基の炭素原子数は、 1乃至 20であることが好ましい。環状アルキル基よりも鎖状アルキル基の方が好まし い。 鎖状アルキル基は、 分岐を有していてもよい。 アルキル基の例には、 メチル、 ェチル、 ィソプロピル、 ブチル、 se c—ブチル、 t e r t—プチル、 ペンチル、 t ert—ペンチル、 へキシル、 ォクチル、 2—ェチルへキシル、 t e rt—ォ クチル、 デシル、 ドデシル、 へキサデシル、 ォク夕デシル、 シクロプロピル、 シ クロペンチル、 シクロへキシルおよびビシクロ [2， 2, 2] ォクチルが含まれ る。

In the general formula (I), the benzene groups a and b may have a substituent. Examples of the substituent 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. Examples of 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. Examples of the 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. Examples of the 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. Examples of aryl groups include phenyl and naphthyl. The aryl group may have a substituent. Examples of 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. One NH one S0 ₂ — R, one CO— NR ₂ , one 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 heterocyclic group contained in the ultraviolet absorbing monomer of the present invention preferably has a 5- or 6-membered heterocyclic group. Examples of 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.

-General formula (Π

In the general formula (II), 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. Examples of 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_〇 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.

 In the general formula (II), 1 L— is a single bond or 10 —. One L1 is preferably a single bond.

In the general formula (Π), the benzene ring c may have a substituent. Examples of the substituent 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ヽ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 substituted alkenyl group or an aryl group. General formula

In the general formula (III), the benzene ring d and the triazine ring e may have a substituent. Examples of the substituent 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, - S- R, one CO- R, one CO- 0 one R, _0 - CO- R, one S0_R, one S0 ₂ - R, one _{NR 2, - NH- CO- R,} -NH-S0 _2- , one CO— NR ₂ , one S〇 ₂ — NR ₂ —, -NH-C0-0-R And it includes 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.

 The substituent on the triazine ring e is preferably an aryl group, more preferably phenyl, and most preferably 0-hydroxyphenyl.

 In the general formula (III), another aromatic ring or hetero ring may be condensed to the benzene ring d. Examples of the condensed aromatic ring include a benzene ring and a naphthylene ring. Examples of 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.

In the general formula (IV), 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. , Alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, aryl group, heterocyclic group, —0-R, —S—R, —CO—R, one CO—0—R, one 0— C 0- R, one SO- R, one S0 ₂ - R, one NR _2, one NH- C0_R, one NH- S0 ₂ _R, one _{C0_NR 2, - S0 2 - NR} 2 -, one NH- C 0- 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. General formula (V)

R ¹ R ²

 \ /

 C = C

 / \

Ar ² R ^{3 In the} general formula (V), 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. Examples of the 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"ヽ- 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.

In the general formula (V), R ¹ is a hydrogen atom or an alkyl group.

In the general formula (V), 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. Examples of 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ヽ-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.

General formula (VI)

In the general formula (VI), 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. Examples of 5- or 6-membered 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.

In formula (VI), 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. And 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. Examples of 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. Examples of 5- or 6-membered substituents include alkyl, substituted alkyl, aryl, 1—R, —S—R, —CO—R, —CO—0—R, — CO-R ヽ one SO— R, one S0 ₂ -R ヽ 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. General formula

In the general formula (VII), R ⁸ is an alkyl group, a substituted alkyl group or an aryl group.

In the general formula (VII), R ⁹ and R ^{1Q each} independently represent a cyano group, one COR ²⁷ , one COOR ²⁸ヽ 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. Examples of 5- or 6-membered rings that function as acidic nuclei include 2-virazoline-1-5-one 璟, virazolidine-1,2,4-dione, rhodanine 璟, hydantoin 2, 2-thiohydantoin 4, and 4-onethione. Hydantoin 璟, 2,4-oxazolidinedione ring, isooxazolone ring, barbidyl acid 璟, 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. Examples of the 5- or 6-membered ring substituent include an alkyl group, a substituted alkyl group, an aryl group, 0—R ヽ —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.

であって、 R^M、 R³⁵、 R³⁶、 R³⁷、 R³⁸および R³⁹は、 それそれ独立 に、 水素原子、 アルキル基またはァリール基であるか、 あるいは、 R³⁸と R³⁹と が結合して、 ベンゼン環またはナフタレン璟を形成する。 In the general formula (VII), 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.

In the general formula (VII), 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.

In the general formula (VII), n is 0 or 1.

In the general formula (VIII), 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璟 or forms a 6-membered ring.

In the general formula (VIII), benzenes h and i are optionally substituted _c substituents such as halogen atom (F, Cl, Br), nitro group, cyano group, sulfo group , An alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group, a heterocyclic group, 10-R, one S-R, one CO-R, -CO-0-R, one 0- C 0 - R, one SO - R, one S0 ₂ - R, one _{NR 2, - NH- CO- R,} -NH-S0 2 one 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.

 In the general formula (VIII), another aromatic ring or hetero ring may be condensed to the benzene rings h and i. Examples of the condensed aromatic group include a benzene ring and a naphthalene ring. Examples of 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. Hereinafter, 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.

く、 0. 0 l〜l//mがより好ましい。 また、 ノズルから吐出させる場合は、 ポリマー微 粒子分散物の吐出安定性をよくするためには、 0. 001~0. 5〃mが好まし

And more preferably 0.01 to l // m. When discharging from a nozzle, 0.001 to 0.5 μm is preferable in order to improve the discharge stability of the polymer fine particle dispersion.

It is diluted with distilled water so that the particle concentration in the lima fine particle dispersion becomes 0.1 to 1% by mass, and a commercially available volume average particle size analyzer (for example, Microtrac UPA (Nikkiso Co., Ltd.) Can be easily measured by Further, the dynamic light scattering method utilizing the laser-Doppler effect is preferable because the particle size can be measured down to a small size. 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.

In the inkjet image recording method of the present invention, as described above, 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. In this case, 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 . In this case, 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. However, when the polymer-fine particle dispersion is applied first, 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. In the ink jet image recording method of the present invention, 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. 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. Next, the colorant contained in the ink composition of the present invention will be described below. Here, 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. In the present invention, each substituent is limited or explained by Hammett's substitution constant and p-value. However, 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. Although 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. 2001-187457, and the crp value of the present invention is the same as that specified therein. In the present invention, and p value are used in this sense. The colorant used in the present invention may be any of a water-soluble dye, an oil-soluble dye or a pigment.

 Examples of the water-soluble and oil-soluble dyes include yellow dyes, magenta dyes, and cyan dyes.

The yellow dye is not particularly limited and may be appropriately selected from known 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; There are quinone dyes such as quinone dyes and the like, and other dyes include quinophthalene dyes, nitro'nitroso dyes, acridine dyes, and acridinone dyes.

 These 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.

 There is no particular limitation on the magenta dye, and it can be appropriately selected from known dyes. For example, 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; for example, 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; dioxazine dyes and the like And condensed polycyclic dyes such as

 These 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. For example, 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.

 These cyan dyes may exhibit cyan only after a part of the chromophore dissociates. In this case, the count cation is an inorganic cation such as alkali metal or ammonium. And organic cations such as pyridinium and quaternary ammonium salts, and polymer cations having these in their partial structures. Examples of the water-soluble dye used in the present invention include direct dyes, acid dyes, food dyes, basic dyes, and reactive dyes. Particularly preferred are:

 CI Direct Red 2, 4, 9, 23, 26, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 21, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247

C.I.Direct violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, skin 101

 CI Direct Yellow 1, 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 86, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 132, 142, 144, 161, 163

 CI Direct Pull 1, 10, 15, 22, 25, 55, 67, 68, 71, 76, 77, 78, 80, 84, 86, 87, 90, 98, 106, 108, 109, 151, 156, 158, 159, 160, 168, 189, 192, 193, 194, 199, 200, 201, 202, 203, 207, 211, 213, 214, 218, 225, 229, 236, 237, 244, 248, 249, 251, 252, 264, 270, 280, 288, 289, 291 CI Direct Black 9, 17, 19, 22, 32, 51, 56, 62, 69, 77, 80, 91, 94, 97, 108, 112, 113, 114, 117, 118, 121, 122, 125, 132, 146, 154, 166, 168, 173, 199

 CI Acid Red 35, 42, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 151, 15 158, 249, 254, 257, 261, 263, 266, 289, 299, 301, 305, 336, 337, 361, 396, 397

 C. I. Acid Violet 5, 34, 43, 47, 48, 90, 103, 126

CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127, 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227

 C. I. Acid Bull 9, 25, 40, 41, 62, 72, 76, 78, 80, 82, 92, 106, 112,

113, 120, 127: I 129, 138, 143, 175, 181, 205, 207, 220, 221, 230, 232, 247s 258, 260, 264, 271, 277, 278, 279, 280, 288, 290, 326

C. I. Acid Plaque 7, 24, 29, 48, 52: 1, 172

 C. I Reactive LEDs 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55

C. I Reactive Bioreets 1, 3, 4 ヽ 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26 ヽ 27, 33, 34

C. I Reactive Yellow 1, 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42

C. I Reactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 17, 18, 19, 21, 25, 26, 27, 28, 29, 38

C. I Reactive Black 4, 5, 8, 14, 21, 23, 26, 31, 32, 34

C. I Basic thread 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35, 36, 38 ヽ 39, 45, 46

C. I Basic Violet 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48

C. I Basic Yellow 1, 2, 4, 11, 13, 14s 15, 19, 21, 23, 24, 25, 28, 29 ヽ 32, 36, 39, 40

C. I Basic Blue 1, 3, 5, 7, 9, 22, 26, 41, 45, 46, 47, 54, 57, 60, 62, 65, 66, 69, 71

C.I. basic black 8, etc. Preferred water-soluble dyes in the present invention are compounds represented by the general formula (AI). Hereinafter, the azo dyes represented by the general formula (A-1) of the present invention will be described in detail.

 General formula (A-I)

In the general formula (A-1), 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.

 Specific examples of 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. Group, nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiosianate Group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, and other electron-withdrawing groups having a crp value of 0.20 or more. Substituted aryl group, hetero group, halogen atom, azo group Or Serenoshianeto group.

The group in which 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, cyclohexenyl), aryl groups (eg, phenyl, 4-t-butylphenyl ブ チ ル 2,4-di-tert-amylphenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-Chenyl, 2-pyrimidinyl, 2-pentazothiazolyl), cyano, hydroxy, nitro, carbonyl, amino, alkyloxy (eg, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy) ), Aryloxy groups (for example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxy-l-bamoyl), and acylylamino groups ( For example, acetoamide, penzamide, 4-1 (3— t— Butyl-4-hydroxyphenoxy) butanamide), alkylamino group (for example, methylamino, butylamino, getylamino, methylbutylamino), anilino group (for example, phenylamino, 2-chloroanilino, ureido group (for example, phenylperide, methylperide, N, N-dibutylperido), a sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, 2-phenoxethylthio), a Arylthio group (for example, phenylthio, 2-butoxy-5-tert-phenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino), sulfonamide group (For example, Amide, benzenesulfonamide, p-toluenesulfonamide), sorbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-getylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl group (for example, methoxycarbonyl, butyl) Hydroxycarbonyl), heterodioxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydrovinyliloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-methoxy) Piperoylaminophenylazo, 2-hydroxy-1 41 B Pano I Ruff enyl § zo), Ashiruokishi group (e.g., § Se butoxy), a force Rubamoiruokishi group (e.g., N- methylcarbamoyl O alkoxy, N Monophenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group

(For example, 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.

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? ~ 18 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 iodine atom and having 1 to 18 carbon atoms.

More preferably, alkyloxycarbonyl group having 2 to 12 carbon atoms, nitro group, cyano group, alkylsulfonyl group having 1 to 12 carbon atoms, arylsulfonyl group having 6 to 18 carbon atoms, carbon number; And a halogenated alkyl group having 1 to 12 carbon atoms. Particularly preferred as 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.

In the general formula (AI), 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 aryloxycarbonyl group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

 Among them, 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. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. Examples of 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. Examples of 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. Examples of 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. As the aryl group, an aryl group having 7 to 12 carbon atoms is preferable. Examples of 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.

R ⁵¹ ~: The heterocyclic groups R ⁵⁶ and Y ¹ represent, include heterocyclic groups and unsubstituted heterocyclic group having a substituent. As the hetero group, a 5- or 6-membered heterocyclic group is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of 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. Examples of 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. Examples of 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. Examples of 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. Examples of 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. Examples of 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. Examples of 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. Examples of the substituent include an alkyl group. Examples of the 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. Examples of 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. Examples of 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. Examples of the substituent include an alkyl group. Examples of 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. Examples of the substituent include an alkyl group. Examples of 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. Examples of 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. As the above heterooxy group, a heterooxy group having a 5- or 6-membered hetero ring is preferable. Examples of the substituent include a hydroxyl group, and an ionic hydrophilic group. Examples of 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 ρ-nitrophenylazo group.

R ⁵¹ or more: 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. Examples of 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. Examples of the substituent include an alkyl group. Examples of the 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. Examples of the substituent include an alkyl group. Examples of the silyloxy group include a trimethylsilyloxy group.ο

R ⁵¹ ~: 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.

R ⁵¹ to: 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. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

R ⁵¹ ~! 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.

R ⁵¹ to: 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. As the above-mentioned acyl group, an acyl group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of 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. As the ionic hydrophilic 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).

In the general formula (A-1), 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 璟 are shown below.

一般式 （A-I) において、 Aは、 5〜8員環を形成するのに必要な非金属原子 群を表す （以下、 Aで表される環を「環 A」という場合がある） 。 環 Aは飽和環で あっても不飽和結合を有していてもよい。前記非金属原子群は、 窒素原子、 酸素 原子、 ィォゥ原子および炭素原子から選ばれる 1種または 2種以上を組み合わせ た群が好ましく、 炭素原子のみからなるのが特に好ましい。

In the general formula (AI), 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.

In the general formula (AI), 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 aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group.

 Among them, 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.

For each of the above groups Z ¹¹ and Z ¹² represent, it is each group and its represented R ⁵¹ to R ⁵⁶ and Y ¹ is it synonymous preferred ranges are also the same. Among the azo dyes represented by the general formula (A-1), an azo dye having a structure represented by the following general formula (Α-Π) is preferable. Hereinafter, the azo dye represented by the general formula (Π- の) of the present invention will be described in detail.

 General formula (A-II)

In the general formula (A-II), 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ヽΖ ^{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 . '

In the general formula (Α-Π), 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 heterocyclic thio group, a sulfinyl group, a phosphoryl group, an acyl group, or an ionic hydrophilic group. Represent.

 Among them, 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.

Specific examples of 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 .

As Z ¹³ and Z ¹⁵ , 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. Are particularly preferable, and among them, a hydrogen atom, an alkyl group and an ionic hydrophilic group are particularly preferable, and an ionic hydrophilic group is most preferable.

As particularly preferred substituents of the azo dye represented by the general formula (A-II), 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 ^½ 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. In addition, as for the preferable combination of the substituents of the compound represented by the general formula (A-II), 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.

However, in the general formula (AI), at least one of 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 (Α-Π) 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 (Α-Π) is more preferably a structure represented by the following general formula (Α-ΙΠ).

 General formula (Α-III)

Formula (Alpha - III) ^{in, X 1, Y \ Z n} ZZ 14, 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.

Particularly preferred 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.

SO3K

19

Sl.T0 / C0df / X3d 80 0 OAV

S0 ₃ K ccl

 (124)

SO3K (125)

 SO3K

(126)

 (127)

CI

CI

OCH

The solubility in water of the oil-soluble dye used in the present invention is not particularly limited.

 Although not limited to the following, preferable specific examples of the oil-soluble dye include, for example, I. Solvent Black 3, 7, 27, 29, 34;

 I. Solvent 'Yellow 14, 16, 19, 29, 30, 56, 82, 93, 162;

 C. I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109,

122, 132, 218;

 C.I.Sorpent Biolate 3;

 I. Solvent Bull 2, 11, 25, 35, 38, 67, 70;

 C. I. Solvent Green 3, 7;

 C.I.Solvent Orange 2 ；

And the like. Among them, particularly preferred are 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.

 In the present invention, a disperse dye can be used as long as it is soluble in a water-immiscible organic solvent. Preferred specific examples thereof include:

 I. Daspasierro I, 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184: 1, 186, 198, 199, 201, 204 , 224, 237;

 I. Daispurs Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119, 163;

 I. Daispurs Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1 , 177, 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356, 362; I. Daispers Violet 33;

I. Daispurs Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224 , 225, 257, 266, 267, 287, 354, 358, 365, 368;

 I. Day Spurs Green 6: 1, 9;

And the like. Particularly preferred oil-soluble dyes include azo and azomethine dyes represented by the following formulas (B-I) and (Β-Π). Dyes of the general formula (II-III) are known as dyes formed from couplers and developing agents by oxidation in photographic materials.

 General formula (B-1) General formula (Β-Π)

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璟基, 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, acyl Represents a carboxyl group or a sulfo 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. B ¹ represents = C (R ⁶³ ) one or = N—, and B ² represents one C ( ⁶⁴ ) = or —N =. BB ² is preferably if not one N = and at the same time, B ¹ is ^{= C (R 63) -,} B 2 gar C (R ⁶⁴⁾ = and further good preferable if made. 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 璟 or a complex 璟 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 .

In the formula (B-1), 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. Examples of heteroatoms in the heterocycle include N, 0, and S. Examples of the saturated heterocyclic ring include a pyrrolidine ring and a morpholine ring. Insatiable The sum heterocycle includes birazol, imidazole, thiazolyl, isothiazole, thiadiazol, thiophene, benzothiazole, benzoxazol, benzoisothiazol, pyrimidine, and pyridine. And a quinoline ring. 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 (Β-Π) 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. Patent 3,973,968, 4,314,023, 4,511,649, European Patents 249,473A and 502,424A Couplers represented by I) and (II); couplers represented by formulas (1) and (2) of JP-A-513,496A (especially Y-28 on page 18); A coupler represented by (I), a force brush represented by general formula (I) in column 45-55 of column 1 of U.S. Pat. No. 5,066,576, and a general description of paragraph 0008 of JP-A-4-274425. The force blur represented by formula (I), the coupler described in claim 1 on page 40 of EP 498,381-1 (especially D-35 on page 18), and the formula (Υ) on page 4 of 447,969A1 (Especially Υ-1 (page 17), Υ-54 (page 41)) 4,476, 219 No. of 36-58 rows of formula column 7 (II) ~ couplers tables in (IV) (particularly [pi-17, 19 (column 17), pi-24 (column 19)).

 Mazen Yu coupler: U.S. Pat. Nos. 4,310,619 and 4,351,897, European Patent 73,636, U.S. Pat. Nos. 3,061,432, 3,725,067, Research Disclosure No. 24220 (1984 No. 24230 (June 1984), JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-Π8034, JP-A-60-33 185951, U.S. Pat.Nos. 4,500,630, 4,540,654, 4,556,630, W088 / 04795, JP-A-3-39737 (L-57 (lower right of page 11), L-68 (page 12, lower right), L-77 (page 13, lower right), EP 456,257 [A-4] -63 (page 134), [A-4] -73, -75 ( 139), 486, 965, M-4, M-6 (page 26), M-7 (page 27), 571,959A, M-45 (page 19), No. (M-1) (p. 6), paragraph No. 4-237263, paragraph 0237, M-22, U.S. Pat. Nos. 3,061,432 and 3,725,067.

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.

 In addition, couplers described in JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3, 30), and EP355, 660A (pages 4, 5, 45, 47) are also useful. is there. Among the dyes represented by the general formula (B-I), as the magenta dye, a dye represented by the following general formula (B-III) is particularly preferably used.

 General formula (B-III)

In the formula, Ζ 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吸弓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. Group, cyano group, carbon number :! Preferred are 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. And 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. Specific examples of such a {structure} include, for example, benzene, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclohexene, pyridine, pyrimidine, pyrazine, and pyridazine.璟, triazine ring, imidazo And a benzimidazole ring, an oxazolyl ring, a benzoxazolyl ring, an oxane ring, a sulfolane ring, and a thiane ring.When these rings further have a substituent, 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. Among the dyes represented by the general formula (Β-Π), as the magenta dye, a dye represented by the following general formula (B-IV) is particularly preferably used.

 General formula (B-IV)

In the formula, 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-Π), and their preferred ranges are also the same. _C L is a β-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.

Among the compounds represented by the general formula (Β-IV), it is preferable that L forms a 5-membered nitrogen-containing heterocyclic ring. Examples of the 5-membered nitrogen-containing heterocycle include an imidazole ring, a triazole II, and a tetrazole ring. Examples of the magenta dye represented by the general formula (BI) or the general formula (Β-Π) will be described below, which are for describing the present invention in detail, and are described below. Is not limited.

 (M-5)

 (M-6)

₂

0, one (n) C ₈ H ₁₇

_Two

6L

 o o OA

SlZ.lO / £ Odf / I3d

08

Sl.T0 / C0df / X3d 80 0 OAV

M-19

, C ₂ H ₄ CN

C _fi 8H ⁿ 17

o C ₁₂ H ₂₅ (n)

o

 CO

! I

O2C2H5

M-35

 M-36

As the 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 (Β-ΠΙ) 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. Among the dyes represented by the general formula (Β-Π), as the cyan dye, a triazo-lazomethine dye having a pyro opening represented by the following general formula (B-V) is particularly preferably used. General formula (B-V)

In the general formula (Β-V), AR ⁶¹ , R ⁶² , B ¹ and B ² have the same meaning as the general formula (B-Π), 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.

Formula (B- V) 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吸弓I group is absorbed Sha one flop Is more preferable. Further, 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-ethylcarbamoyl, N, N-dibutylcarbamoyl), and halogen. 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), and 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. .

) (2G—

) (2G—

e _H 8 |. ₀ ( _u ) 3 _OSHN 2 _[ _ _{| 0} 2 _HOヽ 6 H ^fr O (u)

 (9-0)

 (S-0)

 16

Sl.T0 / C0df / X3d 80 0 OAV

(C-1 8)

(C-9)

CH ₂ CH ₂ NHS 0 ₂ CH ₃ 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.

 Most of organic pigments are classified as dyes and often overlap with dyes. Specific examples include the following.

 (a) Insoluble azo type (naphthol type)

 Brilliant Power Min BS, Rake Carmin: FS, Brilliant Firsts Carredo, Rake Red 4R, Para Red, Permanent Red R, Firth Trade F GR, Rake Bolt 5B, VacuMillion No.1, Vermillion No. 2, Tolujin Marun.

 (b) Insoluble 'azo' (anilide)

 Jiazuero I, First Yello G, First Yello I 10 G, Jiazo Orange, Vulcan Orange, Pyrazolone Red.

 (c) Soluble I, raw azo

Lake Orange, Brilliant Carmine 3B, Brilliant Carmine 6B, Brilliant Scar Blade G, Lake Red C, Lake Red D, Lake Red R, Watching Red, Lake Bordeaux 10B, Bonmar L, Bonmar down M _c (d) Phthalocyanine

 Phthalocyanine Nimble, First Skyplay, Phthalocyanine Green.

(e) Dye lake system

 Yellow lake, Eosin lake, Rose lake, Biored lake, Bunore lake, Green lake, Sevier lake.

 (f) mordant

 Alizarin Lake, Mada Ichiban Ichi Min.

 (g) Healthy dye system

 Induslen based, First Bull I rake (GGS).

 (h) Basic dye lake system ''

 Rhodamine lake, Malachite green lake.

 (i) Acid dye lake

 First Sky Blue, Quinoline Aerolequin, Quinacridone, Dioxazine. The ink composition of the present invention is prepared by dissolving and dispersing or dispersing a dye in an aqueous medium. In particular, when an oil-soluble dye is 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.

 The term "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. Means

 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). , Bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-dimethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate) 2-ethylhexyl diphenyl phosphate, octyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, 2-ethylhexyl phenyl phosphate), benzoic acid ester acid ( For example, 2-ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxy benzoate, amides (eg, N, N— Getyldodecanamide, N, N-getyl laurylamide), alcohols or phenols (isostearyl alcohol ヽ 2,4-ditert-amylphenol, etc.), aliphatic esters (for example, dibutoxystil succinate) Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, triptyl citrate, getylaselate, isostearyl lactate, trioctylcitrate), aniline derivatives (N, N-dibutyl-2-butoxy) _ 5 _ tert-octylaniline, etc.), chlorinated paraffins (paraffins with a chlorine content of 10% to 80%) Fin acids), trimesic acid esters

(Eg, triptyl trimesate), dodecylbenzene, diisopropylnaphthylene, phenols (eg, 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4-)

(4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-DG-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkyl phosphoric acids (for example, di- (2-ethyl) Xyl) phosphoric acid, diphenyl phosphoric acid) and the like.

 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).

 Other examples of compounds having high boiling point organic solvents and methods for synthesizing these high boiling point organic solvents are described in, for example, U.S. Patent Nos. 2,322,027, 2,533,514, 2,772,163 and 2,772,163. No. 2,835,579, No. 3,594,171, No. 3,676,137, No. 3,689,271, No. 3,700,454, No. 3,748,141, Nos. 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209, No. 4,127,413, No. 4,193,802, No. 4,207,393, No. 4,220,711, No. 4,239,851, No. 4,278,757, No. No. 4,353,979, No. 4,363,873, No. 4,430,421, No. 4,430,422, No. 4, 464, 464, No. 4,483,918, No. 4,540,657 No. 4,684,606, No. 4,728,599, No. 4,745,049, No. 4,935,321, No. 5,013,639, European Patent No. 2 76, 319A, 286,253A, 289,820A, 309,158A, 309,159A, 309,160A, 509,311A, 510,576A No. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2,091,124A, Japanese Patent No. 48-47335, No. No. 50-26530, No. 51-25133, No. 51-26036, No. 51-27921, No. 51-27922, No. 51-149028, No. 52-46816, No. 53-1520, No. 53- No. 1521, No. 53-15127, No. 53-146622, No. 54-91325, No. 54-106228, No. 54-118246, No. 55-59464, No. 56-64333, No. 56-81836 No. 59-204041, No. 61-84641, No. 62-118345, No. 62-247364, No. 63-167357, No. 63-214744, No. 63-301941, No. 64-9452, No. 64-9454, 64-68745, JP-A-1-01543, 1-102454, 2-792, 2-4-2239, 2-43541, 4-29237, 4- -No. 30165, It is described in JP-A Nos. 4-232946 and 4-346338.

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. In the present invention, when the colorant and the high boiling point organic solvent are hydrophobic, they are used by emulsifying and dispersing in an aqueous medium. When emulsifying and dispersing, 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. For example, 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) and 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.

 As 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.

When emulsifying and dispersing according to the present invention, various surfactants can be used. For example, 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), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. Also preferred are amoxide-type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide. Further, JP-A-59-157, 6 No. 36, pp. (37)-(38), Research 'Disclosure No. 3 0 8 1 1 9 (1989) The surfactants listed as self-described surfactants can also be used. .

In addition, for the purpose of stabilization immediately after the squeezing, a water-soluble polymer can be added in combination with the above surfactant. As 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. Furthermore, in order to stabilize the dye dispersion, acrylates, methacrylates, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl esters which are substantially insoluble in an aqueous medium. 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-. When these polymers which are substantially insoluble in an aqueous medium are used in combination, 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.

 In the case where an oil-soluble dye is dispersed by emulsification and dispersion to form an aqueous ink, it is particularly important to control the particle size of the dye. It is essential to reduce the average particle size in order to increase color purity and density when forming images by inkjet. Volume average particle size 5 to: L 00 nm is preferred.

 It was also found that the presence of coarse particles plays a very important role in printing performance. In other words, it was found that coarse particles clog the nozzles of the head, or form dirt even if they were not clogged, resulting in non-ejection of ink or ejection failure, which had a significant effect on printing performance. In order to prevent this, it is important to keep the number of particles of 5 / Hi or more in the ink 11 at 10 or less and the number of particles of 1 zm or more in the ink 11 at 100 or less.

As a method for removing these coarse particles, a known centrifugal separation method, a microfiltration method, or the like can be used. 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. As an effective means for reducing the average particle size and eliminating coarse particles, a mechanical emulsifying apparatus can be used.

 As the 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.

 Further, 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.

 For example, 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.

When 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. 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.

 As the drying inhibitor used in the present invention, 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 represented by glycol derivatives, glycerin, trimethylolpropane, etc .; polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl) ether Lower alkyl ethers of alcohols, 2-pyrrolidone, N-methyl_2-pyrrolidone, 1,3-dimethyl-12-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethyl sulfo Ki De, sulfur-containing compounds such as sulfolane, Jiaseton'aru call, multifunctional I 匕合 of such diethanol § Min, and urea derivatives. Of these, 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.

 Examples of the antifungal agent used in the present invention 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).

 Examples of the protective agent 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; In order to improve the stability of the polymer fine particle dispersion and / or the ink, 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. For example, 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. Examples of 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), which is an acetylene-based polyoxetylene oxide surfactant, is also preferably used. Also, amine oxide type amphoteric surfactants such as N, N-dimethyl_N-alkylamine oxide are preferable. Further, 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.

In the present invention, 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. Can be used. In forming an image by the ink jet image recording method of the present invention, as an image receiving material, a known recording material, that is, a plain paper, a resin-coated paper, for example, Japanese Patent Application Laid-Open No. Hei 8-169172, JP-A 8-2 7693, JP-A 2-7 7670, JP-A 7-276 7 89, JP-A 9-32 34 75, JP 62 — 2 3 8 7 8 3 and 10- 15 3 989, 10- 2 1 7 4 7 3 and 10- 2 3 9 9 5 Inkjet papers, finolems, and electronic devices described in 10- 3 3 7 9 4 7 and 10- 2 7 7 9 7 and 10- 3 7 7 9 7 4 Photographic paper, cloth, glass, metal, ceramics, etc. can be used. Hereinafter, the recording paper and the recording film used for forming an image by the ink jet image recording method of the present invention will be described.

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. In addition to these supports, 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. In the present invention, as the support, paper and plastic film laminated on both sides with polyolefin (eg, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used. Polyolefin It is preferable to add a white pigment (eg, titanium oxide, zinc oxide) or a coloring dye (eg, cobalt pull, ultramarine, neodymium oxide) to the polyolefin. The image receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, 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. As the white pigment contained in the image receiving layer, a porous inorganic pigment is preferred, and in particular, synthetic amorphous silica having a large pore area is suitable. As the 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.

 Examples of the aqueous binder contained in the image receiving layer 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. In the present invention, among these, 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. For this purpose, a polymer mordant is preferably used.

Regarding the polymer mordant, JP-A-48-28325, JP-A-54-74430, JP-A-54-124726, JP-A-55-22766, JP-A-55-142339, JP-A-60-23850, JP-A-60-23851, No. 60-23852, No. 60-23853, No. 60-57836, No. 60-60643, No. 60-11 No. 8834, No. 60-122940, No. 60-122941, No. 60-12 No. 2942, No. 60-235134, No. 1-1161236, U.S. Pat.No. 2484430, No. 2548564, No. 3148061, No. 330 9690, No. 4115124, No. 4124386, No. 4193800 No. 4273853, No. 4282305, and No. 4450224. 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. Examples of such a cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiarylammonium chloride polymer, cationic polyacrylamide, and colloidal silica. Among them, 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.

 Examples of the light resistance improver 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.

 An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably {τ} -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. Examples of 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.

 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.

Other components contained in the back coat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent whitening agent, a preservative, and a waterproofing agent. 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. Glass transition temperature Addition of a polymer particle dispersion having a low degree (40 ° C or less) to a layer containing a mordant can prevent cracking and force of the layer. Curling can also be prevented by adding a polymer-particle dispersion having a high glass transition temperature to the back layer.

(Example)

 Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto. Example 1

 (Creating Ink Set 101)

 After adding deionized water to the following ink set 101 component to make 1 liter, the mixture was stirred for 1 hour while heating at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 1 Omo 1/1, and the mixture was filtered under reduced pressure through a microfil filter having an average pore diameter of 0.25 m to prepare a light magenton ink.

 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.

 Magenta dye in the specification (101) 3.75 g Diethylene glycol 15 Og

 37g

Glycerin 130 g Triethylene glycol monobutyl ether 13 Og Surfinol 465 10.5 g Trie norenoamine 6.9 g Penzotriazol 0.08 g PROXEL XL2 3.5 g Polymer fine particle dispersion ((P-1) + (I -1)) 50 g (solid content) By changing the type of dye, the type of additive, and the amount of addition, mazen evening ink, light cyan ink, cyan ink, yellow ink, and black ink are prepared, and The ink set 101 shown in FIG. 4 was created. The dyes listed in the table The unit of the amount of additives and additives used is g / 1. The structures of the dyes used are also shown below.

 Ink set 101

 Light Magenta Light Shea Cyan Yellow Black Zentan

 Dye (101) (101) A-2 A-2 Α-3 A-5

 (g / l) 3.75 15.0 8.75 35.0 14.7 20.0

 Α-4 A-6

 14.0 20.0

 A-7

 20.0

A-3

 21.0 S 'I Cilengericol 150 110 200 130 160 20

 (g / l)

 Urea 37 46 11

 (g / l)

 Glycerin 130 160 150 180 150 120

 (g / l)

 bird;! : Chillenk's Recall 130 140 130 140 180 One Monof * Chill Ether

 (g / l)

 C 'I-Chirengericol I ― ― ― I 230 Monobutyl I-Tel

 (g / l)

 2-pyrrolidone-1 81

 (g / l)

 Surf Inn 465 10.5 11.5 11.1 9.8

 (g / l)

 Surfinole STG 8.5 9.8

 (g / l)

 Birds

 6.9 7.0 6.0 6.3 0.9 17.9

 (g / l)

 He'n / Triabourg 0.08 0.07 0.08 0.08 0.06 0.06

 (g / l)

 Proxel XL2 3.5 1.5 1.1 1.2 1.5 1.1

 (g / l)

* ° Lima-fine particles 50 50 50 50 50 50

 Dispersion (solid content)

(g / l)

次に、 表 5に示すようにポリマー微粒子分散物と紫外線吸収性ポリマ一を変更 する以外は、 ィンクセヅト 1 0 1と同様にインクセヅト 1 0 2〜1 0 9を作成し た。 ポリマ一微粒子分散物は固形分がィンク組成物に対して 5質量％になるよう に添力 Πした。

Next, 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.

 Further, 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. Next, 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.

 The following evaluation was performed about the created sample.

 1) Light fastness (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.

 2) Regarding the heat fastness (weather resistance), 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 case of less than 0% was designated as C.

 3) The water resistance was evaluated by immersing the sample in still water for 10 seconds and rating A when there was no change at all, B when slightly bleeding, and C when there was significant bleeding and reduced image quality.

Tables 5 and 6 show the obtained results. Table 5

Table 6 Sample Light fastness Heat fastness Remarks

No.

 Y C Bk Y M C Bk

 101 A A A A A A A A A The present invention

102 A A A A A A A A A The present invention

1 03 A A A A A A A A The present invention

104 A A A A A A A A A The present invention

105 A A A A A A A A Invention

106 A A A A A A A A A The present invention

107 A A A A A A A A A The present invention

108 A A A A A A A A The present invention

109 BCCABCCB Comparative Example

Example 2

 (Creating an ink set 201)

 8 g of dye (M-7), 40 g of surfactant (manufactured by Kao, trade name Emar 20C), 6 g of high boiling organic solvent (S-1), 10 g of high boiling organic solvent (S-2) and acetic acid It was dissolved in 50 ml of ethyl at 70 ° C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to produce an oil-in-water type coarse particle dispersion.

 Next, 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.

 After adding additives such as 140 g of diethylene glycol, 64 g of glycerin and urea to the fine emulsion of the oil-soluble dye obtained as described above, the dispersion of polymer fine particles (P-1) is added to the ultraviolet absorbing polymer. (1) Add 20% by mass of (I-pl), add 90 Oml of deionized water, and adjust the pH to 9 with KOH 10 mol / l to prepare a light magenta ink according to Table 7. did. 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.

Furthermore, the type of dye used, the amount of high-boiling organic solvent, and the type of various additives were changed, and the amount was changed, and magenta ink, light cyan ink, cyan ink, yellow ink, and black ink of ink set 201 shown in Table 7 were changed. An ink was prepared. The amounts of all compounds shown in the table are g / 1. The structures of the high-boiling organic solvents and dyes used are also shown below. Table 7 Ink set 201

 Light maze magenta light cyan cyan yellow black

,

Vg / U .0U 20.0 9.3 37.2 2.1.2 C ™ 2 18.6

 1 i¾¾P approx .; medium 1.52 b./o 27.0 19./4 30.6

(g / l) S-2 6.25 25.52 11.9 47.6 34.7 53.8 Emar 20C 25.0 100 46.5 186.0 136.0 211.0

(g / l)

 S 'I Clenk' recall 87.5 87.5 87.5 87.5 87.5 87.5

(g / l)

 Urea 46.0 46.0 46.0 46.0 46.0 46.0

(g / l)

 `` Vaseline 40.0 40.0 40.0 40.0 40.0 40.0

(g / l)

 bird;! : Tano-lamine 7.5 7.5 7.5 7.5 7.5 7.5

(g / l)

 Henso triazole 0.075 0.075 0.075 0.075 0.075 0.075

(g / l)

 Proxel XL2 2.5 2.5 2.5 2.5 2.5 2.5

(g / l)

Holima-fine particles 50 50 50 50 50 50 Dispersion (solid content)

 (g / l)

Add deionized water to make "!

次に、 表 8に示すようにポリマ一微粒子分散物と紫外線吸収性ポリマ一を変更 する以外は、 ィンクセヅト 2 0 1と同様にインクセヅト 2 0 2〜2 0 9を作成し た。 ポリマ一微粒子分散物は固形分がィンク組成物に対して 5質量％になるよう に添カ卩した。

Next, as shown in Table 8, 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.

 Further, 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. Next, 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.

 The same evaluation as in Example 1 was performed on the obtained sample. Tables 8 and 9 show the obtained results. Table 8

Table 9

Example 3

 (Create ink set))

 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 μm to prepare a light magenta ink.

 Mazen evening dye in the description (101) 3.75 g diethylene glycol 150 g

37 g Glycerin 130 g Triethylene glycol monobutyl ether 130 g Sulfanol 465 10.5 g Triethanolamine 6.9 g Penzotriazole 0.08 g PR0XEL XL 23.5 g Further dye types and additives By changing the type and amount of addition, the magenta ink, light cyan ink, cyan ink, yellow ink, and black ink can be adjusted. The ink set A shown in Table 10 was prepared. The unit of the amount of the dye or additive used in the table is g / 1. Further, the structure of the dye represented by the same symbol as in Example 1 is the same as that shown in Example 1. Table 10

 Ink set A

 Rai 1 1 Ma- !, No-no-no-no I, Nono T Π- Nofino Ιί ノ

 U ri / \ Δ A-3 A-5 ./5 15.0 8.0 35.0 14.7 20.0

 A-4 A- 6

14.0 20.0

 A-7

20.0

A- 3

21.0 Soechlenocricor 150 110 200 130 160 20

 Referee

 Tea / 4o

 Vg / l

No νΤΣ ¹ nono 1 1 inU 1 I ou 1 1 lou 120

 No

I OU Jl Les Gericols 1

I OU

 Monobutyl ether

 (e / l)

 'Ethylenek' recall 230 Monobutyl ether

 (g / l)

 2-pyrrolidone 81

(g / l)

 The Finolls 465 10.5 11.5 11.1 9.8

 (g / l)

 Safinolol STG 8.5 9.8

(g / l)

 Trietano-lamine 6.9 7.0 6.0 6.3 0.9 17.9

(g / l)

 Henzotriazole 0.08 0.07 0.08 0.08 0.06 0.06

(g / l)

 Proxel XL2 3.5 1.5 1.1 1.2 1.5 1.1

(g / l) Next, an image was printed on an inkjet paper photo glossy paper EX manufactured by Fuji Photo Film Co., Ltd. using an inkjet printer Yuichi PM770C (ink set A) manufactured by Epson. E [Immediately after printing 3 times, add 20% by mass of the UV-absorbing polymer (I-pi) to the polymer particle dispersion P-1 (dispersion particle size 0.2 m) so that the solid content becomes 5% by mass. Dilute the solution diluted with deionized water with an ink jet pudding

 I I O

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.

As shown in Table 11, 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. When 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 prepared sample was evaluated in the same manner as in Example 1. Tables 11 and 12 show the obtained results. Table 1 Sample polymer fine particles UV absorption Water resistance Remarks

 No. Dispersion polymer

 301 P-1 I—pi A The present invention

 302 P-2 I -p3 A The present invention

 303 P— 9 Π-ρ1 A The present invention

 304 Π-ρ1 A The present invention

305 PP-1 V— pi A The present invention

 306 PP-3 VI—pi A The present invention

307 PP-8 I- _P 1 A The present invention

 308 I -p2 A The present invention

309 C Comparative example Table 1 2

Example 4

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 same evaluation as in Example 1 was performed on the obtained sample. The obtained results are shown in Tables 13 and 14.

Table 13

Table 14

 Sample Light fastness Heat fastness Remarks

No.

 Y M C Bk Y M C Bk

 401 A A A A A A A A Invention

402 A A A A A A A A A Present invention

403 A A A A A A A A A The present invention

404 A A A A A A A A A The present invention

405 A A A A A A A A A The present invention

406 A A A A A A A A A The present invention

407 A A A A A A A A The present invention

408 A A A A A A A A A The present invention

409 BCCABCCB Comparative Example

Example 5

 (Create InkSet B)

 8 g of the dye (M-7), 40 g of a surfactant (manufactured by Kao, trade name: Emar 20 C), 6 g of a high-boiling organic solvent (S-1), 10 g of a high-boiling organic solvent (S-2) and acetate Chill was dissolved in 50 ml at 70 ° C. To this solution, 500 ml of deionized water was added while stirring with a magnetic mixer to prepare an oil-in-water type coarse particle dispersion.

 Next, 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.

 After adding additives such as 140 g of diethylene glycol, 64 g of glycerin and urea to the fine emulsion of the oil-soluble dye obtained as described above, 900 ml of deionized water is calored, and the pH is adjusted with KOH 1 Omo 1Z1. = 9, the light magenta ink according to Table 15 was prepared. The average particle size of the obtained ink was 51 nm as measured by using Microtrac UPA (manufactured by Nikkiso Co., Ltd.).

 Table 15 shows the composition of the final composition after solvent evaporation.

Further, the type of dye used, the amount of high-boiling organic solvent, and the type and amount of various additives were changed, and the magenta ink, light cyan ink, cyan ink, yellow ink, and black ink of ink set B shown in Table 15 were changed. Prepared. The amounts of all compounds shown in the table are g / 1. Further, the structures of the high boiling point organic solvent and the dye represented by the same symbols as in Example 1 are the same as those shown in Example 1. Table 15

 Ink set B

次に、 富士写真フィルム社製インクジェットペーパーフォト光沢紙 E Xに、 E P S O N社製インクジェットプリン夕一 P M 7 7 0 C (インクセヅト B ) を用い て画像を印刷した。 印刷した直後に、 ポリマー微粒子分散物 P—1 (分散粒子サ ィズ 0 . 2〃m) に紫外線吸収性ポリマー （ I _ p 1 ) を 2 0質量％添加し固形 分 5質量％になるように脱ィォン水で希釈した液をインクジェットプリン夕一で 吐出させ、 画像上に固形分の塗布量が 0 . 5 g/m²となるように塗布し、 サン プル 5 0 1を作成した。

Next, 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. Immediately after printing, 20% by mass of an ultraviolet absorbing polymer (I_p1) is added to the polymer fine particle dispersion P-1 (dispersion particle size: 0.2 μm) so that the solid content becomes 5% by mass. Then, 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.

As shown in Table 16, the types of the polymer fine particle dispersion and the UV-absorbing polymer were changed, and other than that, Samples 502 to 309 were prepared in the same manner as Sample 501. The amount of UV-absorbing polymer added is 20 times the amount of the original polymer-fine particle dispersion. %. When two or more polymer fine particle dispersions were used, they were used in equal amounts so that the total coating amount was 0.5 gZm ^{2 in} solid content.

 The same evaluation as in Example 1 was performed on the obtained sample. The obtained results are shown in Table 16 and Table 17. Table 16

Table 1 Ί

 sample

 Light fastness Heat fastness Remarks

 No.

 Y M C Bk Y M C Bk

501 A A A A A A A A Invention

502 A A A A A A A A The present invention

503 A A A A A A A A A The present invention

504 A A A A A A A A A The present invention

505 A A A A A A A A The present invention

506 A A A A A A A A Invention

507 A A A A A A A A A The present invention

508 A A A A A A A A A The present invention

509 BCCBBCCC Comparative Example Example 6

 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

 V V

2 and then immediately print the image using ink set B

 N

Sample 6 01 was created.

 As shown in Table 18, the types of the polymer fine particle dispersion and the UV-absorbing polymer were changed, and the other samples were made in the same manner as sample 61 to prepare samples 62 to 609

 a

did. TO

 The same evaluation as in Example 1 was performed on the obtained sample. Tables 18 and 19 show the obtained results. Table 1 8 Sample Polymer Fine Particle Ultraviolet Absorption Water Resistance Remarks

 No. Dispersion polymer

 601 P- 1 I -P1 A ''

 602 P-3 I-1 p2 A The present invention

 603 P-10 Π -ρ1 A The present invention

 604 Π -ρ1 A The present invention

605 PP-1 V -p1 A The present invention

 606 PP-4 VI-p1 A The present invention

 607 PP-7 I -p1 A The present invention

 608 PP-1A The present invention

 PP- 1 2

609 B Comparative example

Table 19

From the above, it can be seen that 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.

Claims

The scope of the claims 1. An ink composition containing a colorant and a polymer-fine particle dispersion, wherein the polymer fine particle dispersion has at least one selected from the group consisting of compounds represented by the following general formulas (I) to (VIII): An ink composition comprising a polymer having the formula: General formula (I)

In the formula, the benzene rings a and b may have a substituent ₍ General formula (II

 In the formula, A is an aryl group or an aromatic heterocyclic group; —L— is a single bond or 10—; and the benzene ring c may have a substituent.

In the formula, the benzene ring d and the triazine ring e may have a substituent; the aromatic ring d may be condensed with another aromatic or heterocyclic ring.

 In the formula, the benzene ring: f and g may have a substituent. General formula (V)

Wherein Ar ² is an aryl group or an aromatic heterocyclic group; R ¹ is a hydrogen atom or an alkyl group; R ² and R ³ are each independently a cyano group, shall apply in CO R ^13, one COOR ^14, one CONR ¹⁵ R ^16, one S 0 ₂ R ¹⁷ or a _{^{S 0 2 NR 18 R 19,}} R 13 ~R 19 is therewith it independently, a hydrogen atom, an alkyl group Or a substituted alkyl group or an aryl group, or R ² and R ³ combine to form a 5- or 6-membered ring. General formula (VI)

In the formula, 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- or 6-membered ring. forming a; R ⁶ and R ^7, it it independently, Shiano ^{group, - COR 2 °, - COOR} 21, a mere CONR ^{22 23} s -S0 ₂ R ²⁴ or a S0 ₂ NR ²⁵ R ^26, R ^{20 to} 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 I do. -General formula (VII)  Y 1  : CH— CH: ^{X to} N two n  R In \ _P-type, R ⁸ is an alkyl group, a substituted alkyl group or Ariru group; R ⁹ and independently, Shiano group, - COR ^27, one ^{COOR 28, -CONR 29 R 3fl,} - a S0 ₂ R ³¹ or a _{^{S0 2 NR 32 R 33, R}} 27 ~R 33 is therewith it independently, a hydrogen atom, an alkyl group, a substituted alkyl group or an Ariru group, or, R ⁹ and R by bonding and ^1Q, form a 5- or 6-membered ring; single X~Y- ^{is, -CR 34 R 35 _CR 36 R} 37 - or a CR ³⁸ = CR ³⁹ - and a, R ³⁴ ~ R ³⁹ is independently a hydrogen atom, an alkyl group or an aryl group, or R ³⁸ and R ³⁹ combine to form a benzene ring or a naphthylene group; one 0-one S - one ^{NR 40 -, _CR 41 R 42} - or a CH-CH- a a: ⁰ alkyl group, a substituted alkyl group or Ariru group Ri, R ⁴¹ and R ^42, it it independent, is hydrogen or an alkyl group; n is 0 or 1. General formula (VIII)

In the formula, R ¹¹ and R ¹² are each independently a hydrogen atom, an alkyl group or an aryl group, or are combined with R ¹¹ to form a 5-membered or 6-membered ring. The benzene rings h and i may have a substituent; and the benzene rings h and i may be condensed with another aromatic or heterocyclic group.  2. The ink composition according to claim 1, wherein the ink composition contains 0.1 to 10% by mass of a polymer fine particle dispersion.  3. A method for recording an ink jet image, comprising forming an image on an image receiving material using the ink composition according to claim 1 or 2. 4. Simultaneously with or after discharging the ink composition containing the colorant onto the image receiving material to form an image, a solution containing the polymer-microparticle dispersion is applied to the image receiving material. An inkjet image recording method, wherein the polymer fine particle dispersion has, as a partial structure, at least one selected from a group of compounds represented by formulas (I) to (VIII) described in claim 1. An ink jet image recording method comprising a polymer.  5. 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 an image is ejected imagewise onto an image receiving material, wherein the polymer-fine particle dispersion is a general formula according to claim 1. An ink-jet image recording method comprising a polymer having at least one selected from the group of compounds represented by (I) to (VIII) as a partial structure. 6. The inkjet image recording method according to claim 4, wherein the applied amount of the polymer fine particle dispersion is 0.1 to 10 g / m ^{2 in} terms of solid content.  7. The ink jet image recording method according to any one of claims 3 to 5, wherein the image receiving material has an image receiving layer containing a white inorganic pigment.