JP2005220219A - Resin composition, resin composition for color filter base, color filter base, and manufacturing method for the filter base - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition useful in applications covering the whole field of industry, particularly a resin composition which improves the defect of a color filter base by an inkjet method capable of efficiently manufacturing the color filter base in a simple step at a low cost and can manufacture the color filter base having excellent color properties by improving water resistance and moisture resistance, to provide the color filter base using the resin composition and a manufacturing method for the color filter base. <P>SOLUTION: The resin composition comprises at least (1) a fine particle dispersion comprising an oil soluble compound and a hydrophobic polymer, (2) a water soluble resin having heat crosslinking properties, and (3) water, and the resin composition for the color filter base can manufacture the color filter base by the inkjet printing method. A resin having an ethylenically unsaturated double bond in the side chain, that having two types of condensation polymerizable functional groups or that having nucleophilic functional group and an electrophilic functional group is preferred as the water soluble resin having heat crosslinking properties. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a resin composition, a resin composition for a color filter substrate produced by an inkjet printing method, a color filter substrate produced using the resin composition, and a method for producing the same.

  Conventionally, as a color filter substrate, a dyeing method color filter substrate in which a mordant layer made of a hydrophilic polymer such as gelatin, casein, mulled or polyvinyl alcohol is provided on the substrate, and colored pixels are formed with the dye on the mordant layer, In addition, a dispersion method color filter substrate in which a colored pixel is formed by a photolithography method using a resin composition in which a color pigment is dispersed in a transparent resin is known. The former dyeing method can create very fine color patterns, but it requires complicated and cumbersome processes such as anti-dyeing, dyeing, washing, fixing, etc. for each color, resulting in productivity and product yield. However, this method is disadvantageous in terms of cost. In addition, the latter dispersion method is also a disadvantageous method in terms of cost because of the low use efficiency when photolithography is performed after the entire surface of the substrate is coated with an expensive resin composition by spin coating or the like. .

On the other hand, in order to meet the demand for a color filter substrate that can be manufactured at a low cost when viewed from the device side by increasing the efficiency of using colored materials in a simple process, the production of a color filter substrate using an inkjet printing method is proposed. (For example, see Patent Documents 1 to 3).
However, a resin composition for drawing using an ink jet printing technique is generally configured based on a water-soluble material. Therefore, the resin composition has high solubility in water, and the color filter substrate having a colored pixel formed by such a resin composition has sufficiently satisfactory resistance in terms of water resistance and moisture resistance. There wasn't.

  The colored pixels provided on the color filter substrate are usually formed using a composition of a specific colorant such as a dye or pigment and an appropriate resin, binder, polymer, or additive. It lacks resistance to solvents and chemicals, while pigments have problems of fine dispersion, dispersion stability, transparency, absorption spectrum or transmission spectrum profile sharpness and lack of diffusivity. In this regard, by using soluble pigment precursors that are acted upon to produce nanometer-sized insoluble pigment particles by chemical, thermal, photolytic means, laser or other radiation, and Coloring materials that combine the advantages of pigments (the solubility of dyes and the weather resistance of pigments) have been proposed (see, for example, Patent Documents 4 and 5).

  However, when the colorant disclosed above is used, it is possible to uniformly disperse the pigment precursor at a high concentration in the polymer film of the colored layer constituting the color filter. When converted into insoluble pigment particles in a polymer film by chemical, thermal, photolytic, or irradiation-inducing means, desorption due to volatilization of a portion of the precursor occurs, resulting in a non-uniform reduction in film thickness Bring. That is, in the case of the above-mentioned soluble pigment precursor, generally, a bulky soluble functional group is introduced to provide solubility in a solvent, and the bulky functional group is eliminated to form an insoluble pigment. Because of the mechanism, the tendency is particularly remarkable. Further, when these detached functional group residues are present in a large amount in the film, there is a concern about the influence. For the above reasons, it is difficult to apply to a field where dimensional accuracy of a color filter or the like, particularly smoothness of a coating film is required.

  In addition, in order to avoid the above problems, when converted to an insoluble pigment in a solvent before forming a coating film, coagulation precipitation due to the drastic decrease in solubility in the solvent accompanying the precipitation of the pigment Since the production of the product occurs, the storage stability is lowered and it becomes difficult to produce a high-concentration solution itself.

Further, as a technology related to a color filter substrate produced by an ink jet printing method, (1) a resin composition for a color filter substrate comprising a specific water-soluble vinyl resin, a color material and water (for example, Patent Document 6) (2) A color filter in which a colored pixel layer obtained by converting a pigment solution containing a soluble pigment precursor, a solvent, and an organic substance stabilizer into an insoluble pigment (see, for example, Patent Document 7), 3) an ink-jet ink composition for a color filter comprising a binder component, a pigment, and a solvent containing a solvent component having a boiling point of 180 ° C. to 260 ° C. and a vapor pressure of 0.5 mmHg or less (for example, see Patent Document 8), (4 ) Vinyl resin obtained by copolymerizing a specific hydrophobic vinyl monomer and a vinyl monomer having an anionic or cationic group, and a colorant encapsulating tree Colored resin emulsion comprising fine particles (for example, see Patent Document 9), (5) A curable mixture containing a crosslinkable water-dispersible precursor capable of thermal ink jetting of a crosslinkable acrylic polymer, a crosslinking agent, and a colorant (for example, a patent) Reference 10) is disclosed.
However, in any of the above cases, if the colorant is pigment-based, it takes a great deal of man-hours to make it finer, or the dye-based colorant is inferior in fading resistance, and is accompanied by insolubilization of soluble pigment substances. There are still problems, and the present situation is that an economical, high-quality and robust color filter substrate by the ink jet printing method has not yet been provided.
JP 59-75205 A JP-A 63-235901 JP-A-1-217320 JP-A-7-188234 JP-A-8-6242 JP 2002-318309 A JP 2001-66411 A JP 2002-201387 A JP 2002-356602 A Japanese translation of PCT publication No. 2002-530461

  The present invention has been made to solve the above-described problems of the conventional methods. That is, an object of the present invention is to provide a resin composition useful for general industrial applications (signaments, posters, cards, display materials, etc.). In particular, it can improve the defect of the color filter substrate by ink jet printing method that can be formed in a simple process and has high material efficiency, improve its water resistance and moisture resistance, and reduce the color filter substrate excellent in hue characteristics and light fastness, etc. It aims at providing the resin composition which can be produced simply. A further object of the present invention is to provide a color filter substrate having excellent characteristics as described above and an economical and stable manufacturing method thereof.

Means of the present invention for solving the above-described problems are as follows.
<1> A resin composition comprising at least (1) a fine particle dispersion containing an oil-soluble compound and a hydrophobic polymer, (2) a water-soluble resin having thermal crosslinkability, and (3) water.
<2> The resin composition as described in <1> above, wherein the water-soluble resin having thermal crosslinkability contains a water-soluble resin having an unsaturated double bond in the main chain or side chain.
<3> The water-soluble resin having thermal crosslinkability contains a water-soluble resin having two condensation-polymerizable functional groups in a side chain. Resin composition.
<4> The water-soluble resin having thermal crosslinkability contains a water-soluble resin having a nucleophilic functional group and an electrophilic functional group in a side chain. The resin composition in any one.
<5> The above <1> to <4>, wherein the fine particle dispersion has an average particle size of 0.01 to 0.5 μm and a specific gravity of 0.9 to 1.2. A resin composition according to claim 1.
<6> The resin composition according to any one of <1> to <5>, wherein the resin composition has a viscosity of 30 mPa · s or less.
<7> The resin composition according to any one of <1> to <6>, wherein the resin composition has a surface tension of 20 to 55 mN / m.
<8> The resin composition according to any one of <1> to <7>, wherein the oil-soluble compound is an oil-soluble dye.
<9> The resin according to <8>, wherein the oil-soluble compound is an azo dye having at least one heterocyclic ring, or a phthalocyanine dye having at least a —SO— or —SO ₂ — bond. Composition.
<10> A resin composition for a color filter substrate, which is produced by an inkjet printing method using the resin composition according to any one of <1> to <9> above.
<11> (1) A step of providing a pixel layer by an inkjet printing method using the resin composition for a color filter substrate according to <10> above on a transparent substrate, and (2) a step of curing the pixel layer by a heat treatment A method for producing a color filter substrate, comprising:
<12> A color filter substrate manufactured by the method according to <11> above.

The resin composition of the present invention is an aqueous composition preferable for safety and environmental suitability, and a coating film formed by heat treatment is a robust, tough, heat-resistant and useful composition. Ink of the present invention using such a resin composition Ink for inkjet printing has ejection stability, and a colored pixel formed by heat treatment while using a water-soluble resin is excellent in water resistance, moisture resistance and heat resistance. Thus, when a color filter substrate is produced using the ink (resin composition) of the present invention, a color filter substrate having characteristics excellent in water resistance, heat resistance, and fading can be obtained.
The method for producing a color filter substrate using the ink (resin composition) of the present invention is to produce a color filter substrate excellent in water resistance and heat resistance with good productivity and at low cost by the inkjet printing method. Is possible.

The resin composition of the present invention comprises at least (1) a fine particle dispersion containing an oil-soluble compound and a hydrophobic polymer, (2) a water-soluble resin having thermal crosslinkability, and (3) water. It is a resin composition.
In particular, the resin composition of the present invention is useful as an ink (resin composition) for a color filter substrate produced by an ink jet printing method, and includes (1) a fine particle dispersion containing at least an oil-soluble compound and a hydrophobic polymer. (2) a water-soluble resin having thermal crosslinkability, and (3) water.
The method for producing a color filter substrate of the present invention includes (1) a step of providing a colored pixel layer on a transparent substrate by the ink jet printing method using the above resin composition, and (2) heat treatment of the colored pixel layer. And a step of curing. Furthermore, the color filter substrate of the present invention is manufactured by the above manufacturing method.
Hereinafter, the resin composition, the color filter substrate, and the production method thereof of the present invention will be described in detail. However, the present invention is not limited to these explanatory items, exemplified compounds, and the like.

(Water-soluble resin with thermal crosslinkability)
First, the water-soluble resin having thermal crosslinkability used in the present invention will be described.
The water-soluble resin having thermal crosslinkability of the present invention is a resin having a functional group or a functional site capable of causing a crosslinking reaction by heating at least by using a water-soluble resin as a skeleton. Examples of the water-soluble resin having such a skeleton include, for example, a polyvinyl alcohol resin that is a resin having a hydroxy group as a hydrophilic structural unit [for example, polyvinyl alcohol (PVA), acetoacetyl-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, Anion-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, polyvinyl acetal, etc.], cellulose resin [for example, methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), hydroxypropyl cellulose (HPC), Hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, etc., chitins, chitosans, starches, resins having ether bonds [Examples For example, polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyvinyl ether (PVE), etc.], resins having a carbamoyl group [for example, polyacrylamide (PAAM), polyvinyl pyrrolidone (PVP), polyacryl Acid hydrazide, etc.].

  As said water-soluble resin of this invention, a water-soluble vinyl-type resin can be mentioned suitably from a viewpoint of manufacture aptitude. Further, as such a water-soluble vinyl resin, a vinyl monomer (A) represented by the following general formula (1), a vinyl monomer having a carboxyl group, an acyl halide group or an acid anhydride group Preferable examples include body (B) and any binary or ternary copolymer comprising a vinyl monomer (C) having a hydroxyl group, a sulfanyl group or an amino group.

〔一般式（１）において、Ｒは水素原子又はアルキル基を表し、Ａｒは芳香族基又は脂肪族基を表し、Ｘは単結合、−ＣＯＯ−、−ＣＯＮＨ−を表し、Ｙは単結合、−（ＣＨ₂）_n−、−（ＣＨ₂Ｏ）_n−、−（ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂）−、を表し、ここでｎは１〜３の整数を表す。〕

[In General Formula (1), R represents a hydrogen atom or an alkyl group, Ar represents an aromatic group or an aliphatic group, X represents a single bond, —COO—, —CONH—, Y represents a single bond, _{- (CH 2) n -,} - (CH 2 O) n -, - (CH 2 CH (OH) CH 2) -, it represents, where n is an integer of 1-3. ]

  Examples of the vinyl monomer (A) represented by the general formula (1) include styrene, α-methylstyrene, divinylbenzene, 2-phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and triethoxy. Examples include phenol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and N-benzyl (meth) acrylamide.

Examples of the vinyl monomer (B) having a carboxyl group, an acyl halide group, and an acid anhydride group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and halides and anhydrides thereof. Etc.
Examples of the vinyl monomer (B) having a hydroxyl group, a sulfanyl group, or an amino group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and corresponding sulfanyl group substitution products. And amino group-substituted products.

  The water-soluble vinyl resin of the present invention may be one obtained by further copolymerizing the above vinyl monomers (A), (B) and (C) with other vinyl monomers. Here, the other vinyl monomer to be copolymerized may be any vinyl monomer having a vinyl group and can be copolymerized. For example, vinyl monomers such as acrylonitrile, allylamine, vinylamine, vinyl acetate, vinyl propionate, etc. Body, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( Monofunctional (meth) acrylates such as (meth) acrylate and tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, morpholine (meth) Water-soluble (meth) acrylic acid esters such as acrylate, (meth) acrylamide, N-methylol (meth) acrylamide, N- (3- (dimethylamino) propyl) (meth) acrylamide, diacetone (meth) acrylamide, etc. (Meth) acrylamide compounds, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, Multifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, (meth) acrylate oligomers and urethane acrylates Include oligomers such rate oligomer.

  The content of the vinyl monomer (A) in the water-soluble vinyl resin is preferably 5 to 30% by mass. When the content is less than 5% by mass, water resistance of the colored pixel obtained by heat-curing the resin composition may not be sufficiently secured. On the other hand, when the content exceeds 30% by mass, The solubility of the water-based resin in water may decrease.

  The content of the vinyl monomer (B) in the water-soluble vinyl resin is preferably 20 to 50% by mass. If the content is less than 20% by mass, the resin composition may not be sufficiently crosslinked by heating, and the water resistance of the formed colored pixels may be insufficient. On the other hand, when the content exceeds 50% by mass, the water-soluble vinyl resin is easily hydrolyzed by the alkaline solution, and the alkali resistance of the colored pixels may be insufficient.

  The content of the vinyl monomer (C) in the water-soluble vinyl resin is preferably 20 to 60% by mass. When the content is less than 20% by mass, the solubility of the water-soluble vinyl resin in water is lowered, and the viscosity of the resin composition may be too high. On the other hand, when the content exceeds 60% by mass, the water resistance of the colored pixels obtained by heat-curing the resin composition may be insufficient.

  In the water-soluble vinyl resin of the present invention, at least a part of the carboxyl groups contained in the vinyl resin may be neutralized with a compound showing alkalinity in the solution in order to enhance the solubility in water. Good. Examples of the compound exhibiting alkalinity in such a solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, quaternary ammonium compounds such as ammonia or tetramethylammonium hydroxide, and 2- Examples include amine compounds such as amino-2-methyl-1-propanol and 2-dimethylaminoethanol. In particular, it is preferable to use ammonia because the water resistance of the colored pixels formed by heating the resin composition can be further improved.

The water-soluble resin having thermal crosslinkability of the present invention is preferably a water-soluble resin having an unsaturated double bond in the main chain or side chain.
Examples of the water-soluble resin having an unsaturated double bond in the main chain include maleic acid, fumaric acid, itaconic acid, 3,6-endomethylene-tetrahydrophthalic acid, hexachloro-3,6-endomethylene-tetrahydrophthal ( HET) condensation polymerization of unsaturated dicarboxylic acids such as acids and halides and anhydrides of the dicarboxylic acids with dihydric alcohols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-butylene glycol, etc.) A water-soluble resin of the system is preferable.

  Examples of the water-soluble resin having an unsaturated double bond in the side chain include side chains having an ethylenically unsaturated bond, specifically, vinyl group, allyl group, isopropenyl group, 1-propenyl group, 2- Butenyl group, 3-butenyl group, 1,3-butadienyl group, 2-pentenyl group, geranyl group, oleyl group, cycloalkenyl group (for example, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group) And water-soluble resins having a vinylbenzyl group, a cinnamyl group, and the like.

  Here, in order to thermally crosslink the water-soluble resin having an unsaturated double bond in the main chain or side chain, it is desirable to add a peroxide (thermal radical generator) such as benzoyl peroxide. A co-crosslinking agent of a vinyl compound (for example, styrene, vinyl acetate, methyl (meth) acrylate, vinyl toluene, etc.) may be added.

In addition, the water-soluble resin having heat crosslinkability of the present invention is preferably a water-soluble resin having two kinds of condensation polymerizable functional groups in the side chain.
Such a combination of two kinds of condensation polymerizable functional groups includes (1) a carboxyl group and a hydroxyl group, (2) a carboxyl group and an amino group, (3) an acyl halide group and a hydroxyl group, and (4) an acyl halide. Preferred examples include a group and an amino group, (5) a carboxylic acid anhydride and a hydroxyl group, and (6) a carboxylic acid anhydride and an amino group.

The water-soluble resin having thermal crosslinkability of the present invention is preferably a water-soluble resin having a nucleophilic functional group and an electrophilic functional group in the side chain.
Here, the above nucleophilic functional group is a so-called anionoid group, and is a functional group that tends to give electrons to the reaction partner (corresponding to a Lewis base). Specifically, an amino group and an alkyl-substituted amino group (—NH ₂ , —N (R) H, —N (R) R ′), a sulfanyl group and an alkyl-substituted sulfanyl group (—SH, —SR), a hydroxy group And functional groups having an alkoxy group (—OH, —OR) and the like.
On the other hand, the above-mentioned electrophilic functional group is a so-called cationoid group, and is a functional group that tends to receive electrons from a reaction partner (corresponding to a Lewis acid), Specific examples include functional groups having an isocyanate group or an epoxy group.

Moreover, the molecular weight of the water-soluble resin having heat crosslinkability used in the present invention is preferably about 1000 to 30000 in terms of polystyrene-equivalent weight average molecular weight. If the molecular weight is less than 1000, a strong film may not be formed even when the resin composition is heated. If the molecular weight exceeds 30000, the resin composition is stabilized by the inkjet method due to high viscosity. May not be discharged.
In the resin composition of the present invention, the content of the above-mentioned water-soluble resin having thermal crosslinkability is the binder component (that is, the total of the water-soluble resin having hydrophobic polymer, high boiling point organic solvent and heat crosslinkability). ) Is preferably 40% by mass or more, more preferably 50% by mass or more, and most preferably 60% by mass or more. If the content of the water-soluble resin having thermal crosslinkability is less than 40% by mass, the water resistance and solvent resistance of the colored pixels formed on the color filter substrate may be insufficient.

(Oil-soluble compounds)
Next, the oil-soluble compound used in the present invention will be described.
The oil-soluble compound that is one of the components constituting the fine particle dispersion of the present invention includes all water-insoluble compounds and is not particularly limited, and may be a known compound according to the purpose within a range not impairing the effects of the invention. It can be suitably selected from the inside. Examples of such compounds include ultraviolet absorbers, antioxidants, anti-fading agents, liquid crystal compounds, fluorescent compounds, oil-soluble dyes, electron-donating colorless dyes, organic EL materials, and polymers thereof. Can be mentioned.
The oil-soluble compound used in the present invention means a compound that is substantially insoluble in water. Specifically, the solubility in water at 25 ° C. (the mass of the dye that can be dissolved in 100 g of water) is 1 g or less, preferably 0.5 g or less, more preferably 0.1 g or less. Among these, examples of the oil-soluble compound used in the present invention include so-called water-insoluble pigments and oil-soluble dyes, and oil-soluble dyes (oil-soluble dyes) are particularly preferable.

The oil-soluble dye used in the present invention preferably has a melting point of 200 ° C. or lower, more preferably has a melting point of 150 ° C. or lower, and still more preferably has a melting point of 100 ° C. or lower. By using an oil-soluble dye having a low melting point, crystal precipitation of the pigment in the fine particle dispersion and the resin composition is suppressed, and the storage stability of the resin composition is improved.
In the fine particle dispersion and the resin composition of the present invention, one kind of oil-soluble dye may be used alone, or several kinds may be used in combination. In addition, other water-soluble dyes, disperse dyes, pigments, and other colorants may be contained as necessary within the range not impairing the effects of the present invention.

  Examples of oil-soluble dyes that can be used in the fine particle dispersion and resin composition of the present invention include anthraquinone, naphthoquinone, styryl, indoaniline, azo, nitro, coumarin, methine, porphyrin, And azaporphyrin and phthalocyanine dyes. In order to complete an inkjet ink for full-color printing, usually, at least four colors of dyes are required, which are the three primary colors of yellow (Y), magenta (M), and cyan (C) plus black.

  Of the oil-soluble dyes that can be used in the present invention, any yellow dye can be used. For example, phenols, naphthols, anilines, pyrazolones, pyridones, aryl or heteryl azo dyes having open-chain active methylene compounds as coupling components; for example, azomethine dyes having open-chain active methylene compounds as coupling components; Methine dyes such as benzylidene dyes and monomethine oxonol dyes; for example, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, Examples include acridinone dyes.

  Of the oil-soluble dyes that can be used in the present invention, any magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines as coupling components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles as coupling components; for example arylidene dyes, styryl dyes, merocyanine dyes, oxonol dyes Methine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycyclic dyes such as dioxazine dyes, etc. Can be mentioned.

  Among the oil-soluble dyes that can be used in the present invention, any cyan dye can be used. For example, indoaniline dyes, indophenol dyes or azomethine dyes having pyrrolotriazoles as coupling components; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes Phthalocyanine dyes; anthraquinone dyes; for example, aryl or heteryl azo dyes having phenols, naphthols and anilines as coupling components, and indigo / thioindigo dyes.

  Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.

Among the oil-soluble dyes, preferred specific examples include the following, but the present invention is not limited to these.
For example, C.I. I. Solvent Black 3, 7, 27, 29 and 34; I. Solvent Yellow 14, 16, 19, 29, 30, 56, 82, 93 and 162; I. Solvent Red 1, 3, 8, 18, 24, 27, 43, 49, 51, 72, 73, 109, 122, 132 and 218; I. Solvent Violet 3; C.I. I. Solvent Blue 2, 11, 25, 35, 38, 67 and 70; C.I. I. Solvent Green 3 and 7; I. Solvent Orange 2 and the like are preferable.
Among these, the Nubian Black PC-0850, Oil Black HBB, Oil Yellow 129, Oil Yellow 105, Oil Pink 312, Oil Red 5B, Oil Scallet 308, Vali Fast Blue 2606, Oil Blue Blu (Oil S) Hodogaya Chemical Co., Ltd.), Neopen Yellow 075, Neopen Magenta SE1378, Neopen Blue 808, Neopen Blue FF4012, Neopen Cyan FF4238 (manufactured by BASF) and the like are more preferable.

In the present invention, disperse dyes can be used as long as they are soluble in a water-immiscible organic solvent. Preferred specific examples thereof include the following, but the present invention is not limited to these. is not.
For example, C.I. I. Disperse Yellow 5,42,54,64,79,82,83,93,99,100,119,122,124,126,160,184: 1,186,198,199,201,204,224 and 237 C. I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; I. Disperse 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 and 362; I. Disperse violet 33; C.I. I. Disperse 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 and 368; I. Disperse green 6: 1 and 9 are preferable.

As the oil-soluble dye used in the present invention, an azo dye having at least one heterocyclic ring, or a phthalocyanine dye having a linking group of at least —SO— or —SO ₂ — is preferable.
Furthermore, among the oil-soluble dyes, preferred examples include compounds represented by the following general formula (I) (azo dyes) and compounds represented by the following general formula (II) (azomethine dyes). An azomethine dye represented by the following general formula (II) is known as a dye formed by oxidation from a coupler and a developing agent in a photographic material.
Hereinafter, the compounds represented by the general formula (I) and the general formula (II) will be described. At least one of the groups represented by the following general formula (I) and the general formula (II) is described below. A compound having a preferable range shown is preferable, a compound having more groups in a preferable range is more preferable, and a compound in which all groups are in a preferable range is particularly preferable.

In the general formula (I) and general formula (II), R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, cyano Group, hydroxy group, nitro group, amino group, alkylamino group, alkoxy group, aryloxy group, amide group, arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfone Amido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring Thio group, sulfinyl group, phosphoryl group, acyl group, carboxyl Represents a group or a sulfo group.
Among these, R ² is preferably a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group, an aryloxy group, an amide group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, or a sulfonamide group.

In General Formula (I) and General Formula (II), A represents —NR ⁵ R ⁶ or a hydroxy group. A is preferably —NR ⁵ R ⁶ .
R ⁵ and R ⁶ each independently represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. Among these, as R ⁵ and R ⁶ , each independently is preferably a hydrogen atom, an alkyl group and a substituted alkyl group, an aryl group and a substituted aryl group, a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, And a substituted alkyl group having 1 to 18 carbon atoms is most preferred. R ⁵ and R ⁶ may be bonded to each other to form a ring.

In the general formula (II), B ¹ represents ═C (R ³ ) — or ═N—. B ² represents —C (R ⁴ ) ═ or —N═. B ¹ and B ² are preferably not simultaneously -N =, more preferably B ¹ is = C (R ³ )-and B ² is -C (R ⁴ ) =.

In the general formula (I) and the general formula (II), R ¹ and R ⁵ , R ³ and R ⁶ , and / or R ¹ and R ² are bonded to each other to form an aromatic ring or a heterocycle. A ring may be formed.

In this specification, an aliphatic group 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 be branched or cyclic. 1-20 are preferable and, as for the carbon atom number in the said aliphatic group, 1-18 are more preferable.
The aryl moiety of the aralkyl group and substituted aralkyl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
Examples of the substituent of the alkyl moiety in the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl group are the same as the examples of the substituents mentioned for R ¹ , R ² , R ³ and R ^4. It is done.
Examples of the substituent of the aryl moiety in the substituted aralkyl group include the same substituents as those in the following substituted aryl group.

In this specification, the aromatic group means an aryl group and a substituted aryl group. As the aryl group, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.
The aryl moiety in the substituted aryl group is the same as in the above aryl group.
Examples of the substituent in the substituted aryl group include the same substituents as those exemplified for R ¹ , R ² , R ³ and R ⁴ .

In the general formula (I), Y represents an unsaturated heterocyclic group. Y is preferably a 5-membered or 6-membered unsaturated heterocyclic ring. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring. N, O, and S can be mentioned as an example of the hetero atom of a heterocyclic ring.
Examples of the unsaturated heterocyclic ring include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, thiophene ring, benzothiazole ring, benzoxazole ring, benzoisothiazole ring, pyrimidine ring, pyridine ring, and quinoline. A ring or the like is preferable. In addition, the unsaturated heterocyclic group may have the substituents exemplified in R ^{1 to} R ⁴ .

In the general formula (II), X represents a color photographic coupler residue. As the coupler, the following couplers are preferable.
As 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, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,023, 4,511,649, European Patent 249,473A Couplers represented by formulas (I) and (II) of No. 502,424A, and couplers represented by formulas (1) and (2) of No. 513,496A (particularly Y-28 on page 18). A coupler represented by the formula (I) of claim 1 of US Pat. No. 568,037A, a coupler represented by the general formula (I) of lines 45 to 55 of column 1 of US Pat. No. 5,066,576, Paragraph 0008 of 4-274425 Couplers represented by general formula (I), couplers described in claim 1 on page 40 of European Patent 498,381A1 (particularly D-35 on page 18), formula (Y) on page 4 of 447,969A1 (Especially Y-1 (page 17), Y-54 (page 41)), US Pat. No. 4,476,219, column 7, lines 36 to 58, formulas (II) to (IV) (Especially II-17, 19 (column 17), II-24 (column 19)) and the like.

  As magenta couplers, there are US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636, US Pat. Nos. 3,061,432, 3,725,067, Research Disclosure No. . 24220 (June 1984), ibid. 24230 (June 1984), JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, U.S. Pat. No. 500,630, No. 4,540,654, No. 4,556,630, International Publication No. WO88 / 04795, JP-A-3-39737 (L-57 (lower right of page 11), L-68 (12) (Lower right of page), L-77 (lower right of page 13), [A-4] -63 (page 134), [A-4] -73, -75 (page 139) of European Patent 456,257, 486, 965, M-4, -6 (page 26), M-7 (page 27), 571, 959A, M-45 (page 19), JP-A-5-204106, (M-1) (Page 6), M-22 in paragraph 0237 of 4-36263 And the like.

  Examples of cyan couplers include U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, European Patent 73,636, and JP-A-4-204843. CX-1,3,4,5,11,12,14,15 (pages 14-16); C-7,10 (page 35), 34,35 (page 37) of JP-A-4-43345 , (I-1), (I-17) (pages 42 to 43); couplers represented by general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.

  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 (I), the magenta dye is particularly preferably a dye represented by the following general formula (III).

In the general formula (III), Z ¹ represents an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more. Z ¹ is preferably an electron-withdrawing group having a σp value of 0.30 or more and 1.0 or less. Preferable specific substituents include the electron-withdrawing substituents described later, and among them, an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, and a cyano group. Group, 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, more preferably a cyano group and a carbon number An alkylsulfonyl group having 1 to 12 carbon atoms and an arylsulfonyl group having 6 to 18 carbon atoms are more preferable, and a cyano group is particularly preferable.

R < ¹ > -R < ⁶ > is synonymous with the said general formula (I).
Z ² 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. Among them, Q is preferably a group composed of a nonmetallic atom group necessary for forming a 5-membered ring to an 8-membered ring, and more preferably an aromatic group or a heterocyclic group. The 5-membered ring to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. As said nonmetallic atom group, a nitrogen atom, an oxygen atom, a sulfur atom, or a carbon atom is preferable.
Examples of the 5-membered ring to 8-membered ring include benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole. Preferred examples include a ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, an oxane ring, a sulfolane ring, and a thiane ring. When these rings further have a substituent, the substituent may be the above R ^{1 to} R ^The groups exemplified in ⁴ are preferred.
A preferable structure of the dye represented by the general formula (III) is described in JP-A No. 2001-335714.

  Among the dyes represented by the general formula (II), the magenta dye is particularly preferably a dye represented by the following general formula (IV).

In the general formula (IV), G is a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, alkoxy group, aryloxy group, alkylthio group, arylthio group, ester group, amino group, carbamoyl group. Represents a sulfonyl group, a sulfamoyl group, a ureido group, a urethane group, an acyl group, an amide group, or a sulfonamide group.
R ¹ , R ² , A, B ¹ and B ² have the same meaning as in the general formula (II), and preferred ranges thereof are also the same as in the general formula (II).
L represents an atomic group that forms a 5- or 6-membered nitrogen-containing heterocyclic ring, and the atomic group that forms the nitrogen-containing heterocyclic ring includes an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, and an alkoxy group. , Aryl group, oxy group, alkylthio group, arylthio group, ester group, amino group, carbamoyl group, sulfonyl group, sulfamoyl group, ureido group, urethane group, acyl group, amide group, or sulfonamide group Or a condensed ring may be formed with another ring.

In the dye represented by the general formula (IV), A is preferably —NR ⁵ R ⁶ , and L is preferably a 5-membered nitrogen-containing heterocycle, and preferably 5-membered nitrogen-containing heterocycle. For example, an imidazole ring, a triazole ring, a tetrazole ring and the like are preferable.

  Of the dyes represented by the general formula (I) and the general formula (II), preferred examples of the magenta dye include compounds (M-1 to M70) described in JP-A-2003-73598. However, the present invention is not limited to these.

  Although the compound which can be used for this invention is described in Unexamined-Japanese-Patent No. 2001-240763, 2001-181549, 2001-335714 other than the said exemplary compound, it is not limited to these.

The dye represented by the formula (III) of the present invention can be synthesized with reference to, for example, methods described in JP-A Nos. 2001-335714 and 55-161856.
The dye represented by the formula (IV) of the present invention is synthesized by referring to the methods described in, for example, JP-A-4-1267772, JP-B-7-94180, and JP-A-2001-240763. Can do.

  Of the dyes represented by the general formula (II), a pyrrolotriazole azomethine dye represented by the following general formula (V) is particularly preferable as the cyan dye.

In the general formula (V), A, R ¹ , R ² , B ¹ and B ² have the same meaning as in the general formula (II), and preferred ranges thereof are also the same as in the general formula (II). .
Z ³ and Z ⁴ are each independently synonymous with G in the general formula (IV). Z ³ and Z ⁴ may be bonded to each other to form a ring structure.
M is an atomic group capable of forming a 1,2,4-triazole ring condensed with the 5-membered ring of the general formula (V), and one of the two atoms B ³ and B ^{4 in} the condensed part is A nitrogen atom and the other a carbon atom.

Furthermore, among the pyrrolotriazole azomethine dyes represented by the general formula (V), it is more preferable that Z ³ is an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more because the absorption is sharp. Those having an electron withdrawing group having a Hammett substituent constant σ _p value of 0.45 or more are more preferred, and those having an Hammett substituent constant σ _p value of 0.60 or more are particularly preferred.
And the sum of Hammett's substituent constant σ _p values of Z ³ and Z ⁴ of 0.70 or more exhibits an excellent hue as cyan, and is most preferable.

  The pyrrolotriazole azomethine dye represented by the general formula (V) can be used as a magenta dye by changing a substituent, but is preferably used as a cyan dye.

Here, Hammett's substituent constant σp value used in this specification will be described.
Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today.
Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill), “Chemical domain” special edition, 122, 96-103, 1979 (Nankodo).

In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, but this means that it is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, even if the value is unknown in the literature, it also includes a substituent that would be included in the range when measured based on Hammett's law.
In addition, the general formula (I) to the general formula (V) of the present invention include those that are not benzene derivatives. However, as a measure of the electronic effect of the substituent, the σp value is independent of the substitution position. Is used. Therefore, in the present invention, the σp value is used in this sense.

Examples of the electron withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group, a nitro group, an alkylsulfonyl group (for example, a methanesulfonyl group, an arylsulfonyl group (for example, a benzenesulfonyl group), and the like.

Examples of the electron withdrawing group having a Hammett σ _p value of 0.45 or more include, in addition to the above, an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m-chloro group). Phenoxycarbonyl), alkylsulfinyl group (eg, n-propylsulfinyl), arylsulfinyl group (eg, phenylsulfinyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dimethylsulfamoyl), alkyl halide Group (for example, trifluoromethyl) and the like.

As an electron-withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more, in addition to the above, an acyloxy group (for example, acetoxy), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), Halogenated alkoxy groups (for example, trifluoromethyloxy), halogenated aryloxy groups (for example, pentafluorophenyloxy), sulfonyloxy groups (for example, methylsulfonyloxy group), halogenated alkylthio groups (for example, difluoromethylthio), An aryl group (eg, 2,4-dinitrophenyl, pentachlorophenyl) substituted with an electron-withdrawing group having two or more σ _p values of 0.15 or more, and a heterocyclic ring (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl) and the like .

  In addition to the above, examples of the electron withdrawing group having a σp value of 0.20 or more include a halogen atom.

  Among the pyrrolotriazole azomethine dyes in the present invention, preferred examples of cyan dyes include compounds (C-1 to C-9) described in JP-A No. 2003-73598, but the present invention includes these compounds. It is not limited.

  Examples of the dye that can be used in the present invention further include exemplified compounds described in JP-A No. 2001-181547, but the present invention is not limited thereto.

  As the yellow pigment used as the oil-soluble dye of the present invention, a compound (dye) represented by the following general formula (Y-I) is preferable.

  In the general formula (Y-I), A and B each independently represent an optionally substituted heterocyclic group. The heterocyclic ring is preferably a heterocyclic ring composed of a 5-membered ring or a 6-membered ring, and may be a monocyclic structure or a polycyclic structure in which two or more rings are condensed. It may be a ring or a non-aromatic heterocyclic ring. As a hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable.

In the general formula (Y-I), examples of the heterocyclic ring represented by A include 5-pyrazolone, pyrazole, oxazolone, isoxazolone, barbituric acid, pyridone, rhodanine, pyrazolidinedione, pyrazolopyridone, meldrum acid, and these A condensed heterocyclic ring in which a hydrocarbon aromatic ring or a heterocyclic ring is further condensed to the heterocyclic ring is preferred. Among these, 5-pyrazolone, 5-aminopyrazole, pyridone, and pyrazoloazoles are preferable, and 5-aminopyrazole, 2-hydroxy-6-pyridone, and pyrazolotriazole are particularly preferable.

  In the general formula (Y-I), the heterocyclic ring represented by B includes pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, Thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, benzoisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline Etc. are preferable. Of these, pyridine, quinoline, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, isoxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzoisothiazole, thiadiazole, and benzoisoxazole are preferable. Thiophene, pyrazole, thiazole, benzoxazole, benzisoxazole, isothiazole, imidazole, benzothiazole, thiadiazole are more preferable, and pyrazole, benzothiazole, benzoxazole, imidazole, 1,2,4-thiadiazole, 1,3,4 -Thiadiazole is particularly preferred.

  Substituents substituted for A and B are halogen atoms, alkyl groups, cycloalkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, alkoxy groups, aryls. Oxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, Sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfo group Group, an acyl group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group ,, an imide group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group.

  Among the dyes represented by the general formula (Y-I), dyes represented by the following general formulas (Y-II), (Y-III), and (Y-IV) are more preferable.

In the general formula (Y-II), R ¹ and R ³ are a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group, or an ionic hydrophilic group. Represents. R ² represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a carbamoyl group, an acyl group, an aryl group or a heterocyclic group. R ⁴ represents a heterocyclic group.

In the general formula (Y-III), R ⁵ represents a hydrogen atom, a cyano group, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryl group, or an ionic hydrophilic group. Za represents -N =, - NH-, or C (R ¹¹⁾ = represents, Zb and Zc each independently, -N =, or C (R ¹¹⁾ = represents the R ¹¹ is a hydrogen atom Or represents a non-metallic substituent. R ⁶ represents a heterocyclic group.

In the general formula (Y-IV), R ⁷ and R ⁹ are each independently a hydrogen atom, cyano group, alkyl group, cycloalkyl group, aralkyl group, aryl group, alkylthio group, arylthio group, alkoxycarbonyl group, A carbamoyl group or an ionic hydrophilic group is represented. R ⁸ is a hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, alkoxycarbonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, It represents a carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, alkylamino group, arylamino group, hydroxy group, or ionic hydrophilic group. R ¹⁰ represents a heterocyclic group.

The substituents represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ^{9 in the} general formulas (Y-II), (Y-III), and (Y-IV) are described in detail below. Describe.

The alkyl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an alkyl group having a substituent and an unsubstituted alkyl group.
The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group.
Preferable examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, and 4-sulfobutyl.

The cycloalkyl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ 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, and examples of the substituent include ionic hydrophilic groups.
Suitable examples of the cycloalkyl group include cyclohexyl.

The aralkyl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an aralkyl group having a substituent and an unsubstituted aralkyl group.
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Suitable examples of the aralkyl group include benzyl and 2-phenethyl.

The aryl group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , and R ⁹ includes an aryl group having a substituent and an unsubstituted aryl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkylamino group, and an ionic hydrophilic group.
Preferable examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl.

The alkylthio group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an alkylthio group having a substituent and an unsubstituted alkylthio group.
The alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms, and examples of the substituent include ionic hydrophilic groups.
Preferable examples of the alkylthio group include methylthio and ethylthio.

The arylthio group represented by R ¹ , R ² , R ³ , R ⁵ , R ⁷ , R ⁸ and R ⁹ includes an arylthio group having a substituent and an unsubstituted arylthio group.
The arylthio group is preferably an arylthio group having 6 to 20 carbon atoms, and examples of the substituent include an alkyl group and an ionic hydrophilic group.
As said arylthio group, a phenylthio group and p-tolylthio are mentioned suitably, for example.

The heterocyclic group represented by R ² is preferably a 5-membered or 6-membered heterocyclic ring, which may be further condensed. As a hetero atom constituting the heterocyclic ring, a nitrogen atom, a sulfur atom and an oxygen atom are preferable. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. The heterocyclic ring may be further substituted, and examples of the substituent preferably include the same substituents as those described later for the aryl group. Preferred heterocycles include 6-membered nitrogen-containing aromatic heterocycles, among which triazine, pyrimidine and phthalazine are particularly preferred.

Preferred examples of the halogen atom represented by R ⁸ include a fluorine atom, a chlorine atom, and a bromine atom.
The alkoxy group represented by R ¹ , R ³ , R ⁵ , and R ⁸ includes an alkoxy group having a substituent and an unsubstituted alkoxy group.
As the alkoxy group, an alkoxy group having 1 to 20 carbon atoms is preferable, and examples of the substituent include a hydroxyl group and an ionic hydrophilic group.
Suitable examples of the alkoxy group include methoxy, ethoxy, isopropoxy, methoxyethoxy, hydroxyethoxy, and 3-carboxypropoxy.

The aryloxy group represented by R ⁸ includes an aryloxy group having a substituent and an unsubstituted aryloxy group.
The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and examples of the substituent include an alkoxy group and an ionic hydrophilic group.
Preferable examples of the aryloxy group include phenoxy, p-methoxyphenoxy, and o-methoxyphenoxy.
The acylamino group represented by R ⁸ includes an acylamino group having a substituent and an unsubstituted acylamino group.
The acylamino group is preferably an acylamino group having 2 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Preferable examples of the acylamino group include acetamido, propionamido, benzamido and 3,5-disulfobenzamido.

The sulfonylamino group represented by R ⁸ includes a sulfonylamino group having a substituent and an unsubstituted sulfonylamino group.
The sulfonylamino group is preferably a sulfonylamino group having 1 to 20 carbon atoms.
Suitable examples of the sulfonylamino group include methylsulfonylamino and ethylsulfonylamino.

The alkoxycarbonylamino group represented by R ⁸ includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group.
The alkoxycarbonylamino group is preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Preferred examples of the alkoxycarbonylamino group include ethoxycarbonylamino.

The ureido group represented by R ⁸ includes a ureido group having a substituent and an unsubstituted ureido group.
The ureido group is preferably a ureido group having 1 to 20 carbon atoms,
Examples of the substituent include an alkyl group and an aryl group.
Suitable examples of the ureido group include 3-methylureido, 3,3-dimethylureido and 3-phenylureido.

The alkoxycarbonyl group represented by R ⁷ , R ⁸ and R ⁹ includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group.
The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Suitable examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.

The carbamoyl group represented by R ² , R ⁷ , R ⁸ and R ⁹ includes a carbamoyl group having a substituent and an unsubstituted carbamoyl group. Examples of the substituent include an alkyl group.
Preferred examples of the carbamoyl group include a methylcarbamoyl group and a dimethylcarbamoyl group.
The sulfamoyl group represented by R ⁸ includes a sulfamoyl group having a substituent and an unsubstituted sulfamoyl group. Examples of the substituent include an alkyl group.
Preferred examples of the sulfamoyl group include a dimethylsulfamoyl group and a di- (2-hydroxyethyl) sulfamoyl group.

Preferable examples of the sulfonyl group represented by R ⁸ include methanesulfonyl and phenylsulfonyl.
The acyl group represented by R ² and R ⁸ includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 20 carbon atoms, and examples of the substituent include an ionic hydrophilic group.
Preferred examples of the acyl group include acetyl and benzoyl.

The amino group represented by R ⁸ includes an amino group having a substituent and an unsubstituted amino group. Examples of the substituent include an alkyl group, an aryl group, and a heterocyclic group.
Preferable examples of the amino group include methylamino, diethylamino, anilino and 2-chloroanilino.

The heterocyclic group represented by R ⁴ , R ⁶ , and R ¹⁰ is the same as the optionally substituted heterocyclic group represented by B in the general formula (YI), and is preferably a preferable example. Examples, particularly preferred examples are the same as described above.
Examples of the substituent include an ionic hydrophilic group, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkyl or arylthio group, a halogen atom, a cyano group, a sulfamoyl group, a sulfonamino group, a carbamoyl group, and an acylamino group. And the alkyl group and aryl group may further have a substituent.

In the general formula (Y-III), Za represents —N═, —NH—, or C (R ¹¹ ) ═. Zb and Zc each independently represent —N═ or C (R ¹¹ ) ═. R ¹¹ represents a hydrogen atom or a nonmetallic substituent. As the nonmetallic substituent represented by R ¹¹ , a cyano group, a cycloalkyl group, an aralkyl group, an aryl group, an alkylthio group, an arylthio group, or an ionic hydrophilic group is preferable. Each of the substituents is synonymous with each substituent represented by R ¹ , and preferred examples are also the same. Examples of the skeleton of a heterocyclic ring composed of two 5-membered rings contained in the general formula (Y-III) are shown below.

  Examples of the substituent in the case where each substituent described above may further have a substituent include a substituent that may be substituted on the heterocyclic rings A and B of the general formula (Y-I). Can be mentioned.

  Specific examples of the dye represented by the general formula (Y-I) include compounds (Y-101 to Y-155) described in JP-A No. 2003-73598. It is not limited to. These compounds can be synthesized with reference to JP-A-2-24191 and JP-A-2001-279145.

  Furthermore, as the oil-soluble dye suitably used as the oil-soluble dye of the present invention, a compound represented by the following general formula (MI) (hereinafter sometimes referred to as “azo dye”) is preferable. Below, the compound represented by general formula (MI) of this invention is demonstrated.

In the general formula (M-I), A represents a residue of a 5-membered heterocyclic diazo component (A-NH ₂ ).
In B ¹ and B ² , B ¹ represents = CR ¹ -and B ² represents -CR ² =, or one of them represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =.
R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Each group may further have a substituent.
G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, Substituted with acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylarylsulfonylamino group, arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkylthio , An arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted.
R ¹ and R ⁵ , or R ⁵ and R ⁶ may be bonded to form a 5- to 6-membered ring.

The compound represented by the general formula (MI) of the present invention will be described in detail.
In the general formula (M-I), A represents a residue of a 5-membered heterocyclic diazo component (A-NH ₂ ). Examples of the hetero atom of the 5-membered heterocyclic ring include N, O, and S. Preferably, it is a nitrogen-containing 5-membered heterocyclic ring, and the heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.
Examples of preferable heterocyclic ring for A include pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, thiadiazole ring, benzothiazole ring, benzoxazole ring, and benzoisothiazole ring. Each heterocyclic group may further have a substituent. Of these, pyrazole rings, imidazole rings, isothiazole rings, thiadiazole rings, and benzothiazole rings represented by the following general formulas (Ma) to (Mf) are preferable.

R ^{7 to} R ²⁰ in the general formulas (Ma) to (Mf) represent the same substituents as the substituents G, R ^1, and R ² described later.
Among the general formulas (Ma) to (Mf), the pyrazole ring and the isothiazole ring represented by the general formulas (Ma) and (Mb) are preferable, and the most preferable is It is a pyrazole ring represented by the general formula (M-a).
B ¹ and B ² are those in which B ¹ represents = CR ¹ -and B ² represents -CR ² =, or one of them represents a nitrogen atom and the other represents = CR ¹ -or -CR ² =. More preferably, B ¹ represents = CR ¹ -and B ² represents -CR ² =.
R ⁵ and R ⁶ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or It represents a sulfamoyl group, and each group may further have a substituent. Preferable substituents represented by R ⁵ and R ⁶ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group. More preferably, they are a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group. Most preferably, they are a hydrogen atom, an aryl group, or a heterocyclic group. Each group may further have a substituent. However, R ⁵ and R ⁶ are not simultaneously hydrogen atoms.

G, R ¹ and R ² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl Substituted with a group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group, aryl group or heterocyclic group Amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkylsulfonylamino group, arylsulfonylamino group, nitro group, alkylthio group, arylthio group, heterocyclic thio group , It represents an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, or a sulfo group, and each group may be further substituted.

  Preferred substituents represented by G include hydrogen atom, halogen atom, aliphatic group, aromatic group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, alkyl group, aryl group or hetero group. And an amino group substituted with a cyclic group, an acylamino group, a ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylthio group, an arylthio group, and a heterocyclic thio group, more preferably , A hydrogen atom, a halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an amino group substituted with an alkyl group, an aryl group or a heterocyclic group, or an acylamino group, among which a hydrogen atom, an aryl group An amino group and an amide group are most preferred. Each group may further have a substituent.

Preferable substituents represented by R ¹ and R ² include a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a carboxyl group, a carbamoyl group, and a cyano group. Each group may further have a substituent.
R ¹ and R ⁵ , or R ⁵ and R ⁶ may combine to form a 5- to 6-membered ring.
Examples of the substituent in the case where each substituent represented by A, R ¹ , R ² , R ⁵ , R ⁶ , or G further has a substituent include the substituents exemplified for G, R ¹ , and R ^2. be able to.

Hereinafter, the substituents represented by G, R ¹ and R ² will be described in detail.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
An aliphatic group 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 and may form a ring. The number of carbon atoms in the aliphatic group is preferably 1-20, and more preferably 1-16. The aryl part of the aralkyl group and the substituted aralkyl group is preferably phenyl or naphthyl, particularly preferably phenyl. Examples of aliphatic groups include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl, 3-sulfopropyl, 4-sulfobutyl. Group, cyclohexyl group, benzyl group, 2-phenethyl group, vinyl group, and allyl group.

In this specification, an aromatic group means an aryl group and a substituted aryl group. The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The number of carbon atoms of the aromatic group is preferably 6-20, and more preferably 6-16.
Examples of the aromatic group include a phenyl group, a p-tolyl group, a p-methoxyphenyl group, an o-chlorophenyl group, and an m- (3-sulfopropylamino) phenyl group.
The heterocyclic group includes a heterocyclic group having a substituent and an unsubstituted heterocyclic group. The heterocyclic ring may be condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring. The heterocyclic group is preferably a 5-membered or 6-membered heterocyclic group. Examples of the substituent include an aliphatic group, a halogen atom, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfamoyl group, a carbamoyl group, and an ionic hydrophilic group. Examples of the heterocyclic group include 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2-benzoxazolyl group, and 2-furyl group.

Examples of the alkylsulfonyl group and arylsulfonyl group include a methanesulfonyl group and a phenylsulfonyl group, respectively.
Examples of the alkylsulfinyl group and arylsulfinyl group include a methanesulfinyl group and a phenylsulfinyl group, respectively.

  The acyl group includes an acyl group having a substituent and an unsubstituted acyl group. As the 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 amino group includes an amino group substituted with an alkyl group, an aryl group, and a heterocyclic group, and the alkyl group, the aryl group, and the heterocyclic group may further have a substituent. Unsubstituted amino groups are not included. As the alkylamino group, an alkylamino group having 1 to 6 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkylamino group include a methylamino group and a diethylamino group.
The arylamino group 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 alkoxy group includes an alkoxy group having a substituent and an unsubstituted alkoxy group. As the alkoxy group, an alkoxy group having 1 to 12 carbon atoms is preferable. 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 includes an aryloxy group having a substituent and an unsubstituted aryloxy group. As the aryloxy group, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent include an alkoxy group and an ionic hydrophilic group. Examples of the aryloxy group include a phenoxy group, a p-methoxyphenoxy group, and an o-methoxyphenoxy group.

  The acylamino group includes an acylamino group having a substituent. The acylamino group is preferably an acylamino group having 2 to 12 carbon atoms. Examples of the substituent include an ionic hydrophilic group. Examples of the acylamino group include an acetylamino group, a propionylamino group, a benzoylamino group, an N-phenylacetylamino group, and a 3,5-disulfobenzoylamino group.

  The ureido group includes a ureido group having a substituent and an unsubstituted ureido group. The ureido group is preferably a ureido 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-dimethylureido group, and a 3-phenylureido group.

  The sulfamoylamino group 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 group.

  The alkoxycarbonylamino group includes an alkoxycarbonylamino group having a substituent and an unsubstituted alkoxycarbonylamino group. As the alkoxycarbonylamino group, an alkoxycarbonylamino group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonylamino group include an ethoxycarbonylamino group.

  The alkylsulfonylamino group and arylsulfonylamino group include a substituted alkyl and arylsulfonylamino group, an unsubstituted alkyl and arylsulfonylamino group. As the alkyl and arylsulfonylamino groups, alkyl and arylsulfonylamino groups having 1 to 12 carbon atoms are preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl and arylsulfonylamino groups include a methanesulfonylamino group, an N-phenylmethanesulfonylamino group, a benzenesulfonylamino group, and a 3-carboxybenzenesulfonylamino group.

  The carbamoyl group includes a carbamoyl group having a substituent and an unsubstituted carbamoyl 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 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.

  The alkoxycarbonyl group includes an alkoxycarbonyl group having a substituent and an unsubstituted alkoxycarbonyl group. As the alkoxycarbonyl group, an alkoxycarbonyl group having 2 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The acyloxy group includes an acyloxy group having a substituent and an unsubstituted acyloxy group. As the acyloxy group, an acyloxy group having 1 to 12 carbon atoms is preferable. Examples of the substituent include an ionic hydrophilic group. Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.

  The carbamoyloxy group includes a carbamoyloxy group having a substituent and an unsubstituted carbamoyloxy group. Examples of the substituent include an alkyl group. Examples of the carbamoyloxy group include an N-methylcarbamoyloxy group.

  The aryloxycarbonyl group includes an aryloxycarbonyl group having a substituent and an unsubstituted aryloxycarbonyl group. As the aryloxycarbonyl group, an aryloxycarbonyl group having 7 to 12 carbon atoms is preferable. Substituents include ionic hydrophilic groups. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.

  The aryloxycarbonylamino group includes an aryloxycarbonylamino group having a substituent and an unsubstituted aryloxycarbonylamino group. 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 phenoxycarbonylamino group.

  The alkyl, aryl, and heterocyclic thio groups include substituted alkyl, aryl, and heterocyclic thio groups, and unsubstituted alkyl, aryl, and heterocyclic thio groups. As the alkyl, aryl and heterocyclic thio groups, those having 1 to 12 carbon atoms are preferred. Examples of the substituent include an ionic hydrophilic group. Examples of the alkyl, aryl and heterocyclic thio groups include a methylthio group, a phenylthio group, and a 2-pyridylthio group.

  In the present invention, particularly preferred azo dyes are compounds represented by the following general formula (M-II).

In the general formula (M-II), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more. Z ¹ is preferably an electron withdrawing group having a σ _p value of 0.30 to 1.0. Specific examples of preferred substituents include the electron-withdrawing substituents described later, among which an acyl group having 2 to 12 carbon atoms, an alkyloxycarbonyl group having 2 to 12 carbon atoms, a nitro group, and a cyano group. , 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 are preferable. 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 most preferred is a cyano group.

R ¹ , R ² , R ⁵ and R ⁶ have the same meaning as in the general formula (MI).
R ³ and R ⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. Among these, a hydrogen atom, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, and an arylsulfonyl group are preferable, and a hydrogen atom, an aromatic group, and a heterocyclic group are particularly preferable.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. Among them, Q is preferably a group composed of a nonmetallic atom group necessary for forming a 5- to 8-membered ring. This 5- to 8-membered ring may be substituted, may be a saturated ring, or may have an unsaturated bond. Among these, an aromatic group and a heterocyclic group are particularly preferable. Preferred nonmetallic atoms include nitrogen atoms, oxygen atoms, sulfur atoms and carbon atoms. Specific examples of the 5- to 8-membered ring include, for example, a benzene ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, imidazole. And a ring, a benzimidazole ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an oxane ring, a sulfolane ring, and a thiane ring.

Each group described in the general formula (M-II) may further have a substituent. When each of these groups further has a substituent, examples of the substituent include the substituents described in the general formula (MI), the groups exemplified for G, R ¹ and R ² , and ionic hydrophilic groups. Can be mentioned.

Here, Hammett's substituent constant σ _p value used in the present specification will be described in relation to the substituent Z ¹ .
Hammett's rule was established in 1935 by L.L. to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σ _p value and a σ _m value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (McGraw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited to only a substituent having a known value that can be found in the above-mentioned book. Needless to say, it also includes substituents that would be included in the range when measured based on Hammett's rule even if the value is unknown. The general formulas (M-I) and (M-II) of the present invention include those that are not benzene derivatives. However, as a measure of the electronic effect of the substituent, σ _p Use the value. In the present invention, the σ _p value is used in this sense.

Examples of the electron withdrawing group having a Hammett substituent constant σ _p value of 0.60 or more include a cyano group, a nitro group, and an alkylsulfonyl group [eg, methanesulfonyl group, arylsulfonyl group (eg, benzenesulfonyl group)] Can be mentioned.
Examples of the electron withdrawing group having a Hammett σ _p value of 0.45 or more include an acyl group (for example, acetyl group), an alkoxycarbonyl group (for example, dodecyloxycarbonyl group), an aryloxycarbonyl group (for example, m -Chlorophenoxycarbonyl group), alkylsulfinyl group (for example, n-propylsulfinyl group), arylsulfinyl group (for example, phenylsulfinyl group), sulfamoyl group (for example, N-ethylsulfamoyl group, N, N-dimethylsulfuryl group) (Famoyl group) and halogenated alkyl groups (for example, trifluoromethyl group).

The electron withdrawing group having a Hammett substituent constant σ _p value of 0.30 or more includes, in addition to the above, an acyloxy group (for example, acetoxy group), a carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutyl). Rucarbamoyl group), halogenated alkoxy group (for example, trifluoromethyloxy group), halogenated aryloxy group (for example, pentafluorophenyloxy group), sulfonyloxy group (for example, methylsulfonyloxy group), halogenated alkylthio group ( For example, a difluoromethylthio group), an aryl group (for example, 2,4-dinitrophenyl group, pentachlorophenyl group) substituted with an electron withdrawing group having two or more σ _p values of 0.15 or more, and a complex A ring (for example, 2-benzoxazolyl group, 2-benzothiazolyl group, 1-phenyl-2-benzimid Zoriru group) can be exemplified.
Specific examples of the electron withdrawing group having a σ _p value of 0.20 or more include a halogen atom in addition to the above.

As the compound represented by the general formula (MI), particularly preferred combinations of substituents are as follows.
(I) R ⁵ and R ⁶ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfonyl group, or an acyl group, and more preferably a hydrogen atom, an aryl group, a heterocyclic group, or a sulfonyl group. And most preferably a hydrogen atom, an aryl group, or a heterocyclic group. However, R ⁵ and R ⁶ are not both hydrogen atoms.
(B) G is preferably a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an amino group or an amide group, more preferably a hydrogen atom, a halogen atom, an amino group or an amide group, most preferably a hydrogen atom. An amino group or an amide group. (C) A is preferably a pyrazole ring, an imidazole ring, an isothiazole ring, a thiadiazole ring, or a benzothiazole ring, more preferably a pyrazole ring or an isothiazole ring, and most preferably a pyrazole ring.
(D) B ¹ and B ² are each ═CR ¹ —, —CR ² ═, and R ¹ and R ² are each preferably a hydrogen atom, a halogen atom, a cyano group, a carbamoyl group, or a carboxyl group. , An alkyl group, a hydroxyl group and an alkoxy group, more preferably a hydrogen atom, a cyano group, a carbamoyl group and an alkoxy group.

  In addition, with respect to a preferable combination of substituents of the compound represented by the general formula (MI), a compound in which at least one of various substituents is the above-described preferable group is preferable, and more various substituents are A compound that is a preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred.

  Specific examples of the dye represented by the general formula (M-I) include compounds (a-1 to a-27, b-1 to b-6, c-1 described in JP-A No. 2003-73598). -C-3, d-1 to d-4, e-1 to e-4) are preferable, but the present invention is not limited to these.

  As the oil-soluble pigment in the present invention, it is preferable to use a compound represented by the following general formula (CI) (hereinafter sometimes referred to as “phthalocyanine dye”). Below, the compound represented by general formula (CI) is demonstrated.

In the general formula (CI), X ¹ , X ² , X ³ and X ⁴ each independently represent —SO—Z ¹ , —SO ₂ —Z ¹ or —SO ₂ NR ²¹ R ²² . .

Z ¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted Represents a heterocyclic group, particularly preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group Most preferred.

R ²¹ and R ²² are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted Of the aryl group, a substituted or unsubstituted heterocyclic group, particularly preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom A substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group are most preferred. However, both R ²¹ and R ²² are not hydrogen atoms.

The substituted or unsubstituted alkyl group represented by R ²¹ , R ²² and Z ¹ is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Among these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

The cycloalkyl group having a substituent or the unsubstituted cycloalkyl group represented by R ²¹ , R ²² and Z ¹ is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

The alkenyl group having a substituent or the unsubstituted alkenyl group represented by R ²¹ , R ²² and Z ¹ is preferably an alkenyl group having 2 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

The aralkyl group having a substituent or the unsubstituted aralkyl group represented by R ²¹ , R ²² and Z ¹ is preferably an aralkyl group having 7 to 30 carbon atoms. Examples of the substituent include the same substituents as those described later when Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ can further have a substituent. Of these, a hydroxyl group, an alkoxy group, a cyano group, and a halogen atom are preferable.

As the substituent of the aryl group represented by R ²¹ , R ²² and Z ¹ , Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ described later can further have a substituent. The same as the substituent in the case. Preferred substituents include halogen atoms, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, acylamino groups, ureido groups, sulfamoylamino groups, alkyloxycarbonyl groups, alkyloxycarbonylamino groups, sulfonamides. Groups, sulfamoyl groups, carbamoyl groups, sulfonyl groups, acyloxy groups, carbamoyloxy groups, imide groups, heterocyclic thio groups, acyl groups, sulfo groups, quaternary ammonium groups, among them heterocyclic groups, cyano groups, carboxyl groups An acylamino group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, and an acyl group are preferable, and a cyano group, a carboxyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group, an imide group, and an acyl group are more preferable.

The heterocyclic group represented by R ²¹ , R ²² and Z ¹ is preferably a 5-membered or 6-membered ring, and they may be further condensed. Further, it may be an aromatic heterocycle or a non-aromatic heterocycle.
In the following, the heterocyclic groups represented by R ²¹ , R ²² and Z ¹ are exemplified in the form of a heterocyclic ring with the substitution position omitted, but the substitution position is not limited, and for example, pyridine It is possible to substitute at the 2nd, 3rd and 4th positions.
Pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole Benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Among these, an aromatic heterocyclic group is preferable, and preferable examples thereof are exemplified in the same manner as described above. Examples include isothiazole and thiadiazole. These may have a substituent.

Y ¹ , Y ² , Y ³ and Y ⁴ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl 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, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamido group, carbamoyl group, Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic thio group, phosphoryl group, An acyl group, a carboxyl group, or Represents a sulfo group, and each may further have a substituent.

  Among these, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group are preferable. An atom and a cyano group are preferable, and a hydrogen atom is most preferable.

When Z ¹ , R ²¹ , R ²² , Y ¹ , Y ² , Y ³ and Y ⁴ are groups capable of further having a substituent, they may further have a substituent as listed below. Good.

  A halogen atom (for example, a chlorine atom or a bromine atom), a linear or branched alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkyl group having 2 to 30 carbon atoms A linear or branched alkynyl group, a linear or branched cycloalkyl group having 3 to 30 carbon atoms, a linear or branched cycloalkenyl group having 3 to 30 carbon atoms, and more specifically (for example, methyl, ethyl, propyl, Isopropyl, t-butyl, 2-methanesulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), an aryl group (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), A heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), Ano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino groups (eg, acetamide, benzamide, 4- (3-t-butyl-4-hydroxyphenoxy) Butanamide), alkylamino groups (eg, methylamino, butylamino, diethylamino, methylbutylamino), anilino groups (eg, phenylamino, 2-chloroanilino, ureido groups (eg, phenylureido, methylureido, N, N-) Butylureido), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino), alkylthio group (eg, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (eg, phenylthio, 2-butoxy- 5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino group (for example, methoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), carbamoyl Groups (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), sulfonyl groups (eg, For example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyloxycarbonyl groups (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyrani) Ruoxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group ( For example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group (for example, phenoxy) Rubonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6- Thio, 2-pyridylthio), sulfinyl group (eg 3-phenoxypropylsulfinyl), phosphonyl group (eg phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl Groups (for example, acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (for example, carboxyl group, sulfo group, and quaternary ammonium group) and the like.

a ^{1 to} a ⁴ and b ^{1 to} b ⁴ each represent the number of substituents X ^{1 to} X ⁴ and Y ^{1 to} Y ⁴ ; a ^{1 to} a ⁴ each independently represents an integer of 0 to 4; ¹ ~b ⁴ each independently represent an integer of 0-4. However, the sum of a ^{1 to} a ⁴ is 2 or more. Here, when a ¹ ~a ⁴ and b ¹ ~b ⁴ is an integer of 2 or more, or different in each plurality of X ¹ to X ⁴ and Y ¹ to Y ⁴ are the same.

a ¹ and b ¹ each independently represents an integer of 0 to 4 satisfying the relationship of a ¹ + b ¹ = 4, and particularly preferably, a ¹ represents 1 or 2, and b ¹ represents 3 or 2. Of these, a combination in which a ¹ represents 1 and b ¹ represents 3 is the most preferable.

a ² and b ² each independently represents an integer of 0 to 4 satisfying the relationship of a ² + b ² = 4, and particularly preferably, a ² represents 1 or 2 and b ² represents 3 or 2. Of these, a combination in which a ² represents 1 and b ² represents 3 is the most preferable.

a ³ and b ³ each independently represents an integer of 0 to 4 satisfying the relationship of a ³ + b ³ = 4, and particularly preferably, a ³ represents 1 or 2 and b ³ represents 3 or 2. Of these, a combination in which a ³ represents 1 and b ³ represents ³ is the most preferable.

a ⁴ and b ⁴ each independently represents an integer of 0 to 4 satisfying the relationship of a ⁴ + b ⁴ = 4, and particularly preferably, a ⁴ represents 1 or 2, and b ⁴ represents 3 or 2. Of these, a combination in which a ⁴ represents 1 and b ⁴ represents 3 is the most preferable.

M represents a hydrogen atom, a metal element or an oxide thereof, a hydroxide, or a halide.
Preferable examples of M include hydrogen atoms and metal atoms such as Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, Bi and the like can be mentioned. Examples of the oxide include VO and GeO. Examples of the hydroxide include Si (OH) ₂ , Cr (OH) ₂ , Sn (OH) _{2 and the} like. Further, examples of the halide include AlCl, SiCl ₂ , VCl, VCl ₂ , VOCl, FeCl, GaCl, and ZrCl. Among these, Cu, Ni, Zn, Al and the like are particularly preferable, and Cu is most preferable.

  In addition, Pc (phthalocyanine ring) may form a dimer (for example, Pc-MLM-Pc) or a trimer via L (a divalent linking group). May be the same or different.

The divalent linking group represented by L includes an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH -), or a methylene group (-CH ₂ -) is preferred.

  As the compound represented by the general formula (CI), particularly preferred combinations are as follows.

X ^{1 to} X ⁴ are each particularly preferably —SO ₂ —Z ¹ or —SO ₂ NR ²¹ R ²² .

Z ¹ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group Is most preferred.

R ²¹ and R ²² are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, a substituted An aryl group and a substituted heterocyclic group are most preferred.

Y ^{1 to} Y ⁴ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, a carboxyl group, and a sulfo group. In particular, a hydrogen atom, a halogen atom, a cyano group, a carboxyl group, and a sulfo group are preferable, and a hydrogen atom is most preferable.

a ^{1 to} a ⁴ are each independently preferably 1 or 2, and particularly preferably 1. b ^{1 to} b ⁴ are each independently preferably 3 or 2, and particularly preferably 3.

  M represents a hydrogen atom, a metal element or an oxide, hydroxide or halide thereof, and Cu, Ni, Zn, and Al are particularly preferable, and Cu is particularly preferable.

  As for the preferred combination of substituents of the compound represented by the general formula (CI), a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  Among the compounds represented by the general formula (CI), a compound having a structure represented by the following general formula (C-II) is more preferable.

In Formula ^{(C-II), X 11} ~X 14, Y 11 ~Y 18 are each synonymous with ^{X 1 ~X 4, Y 1 ~Y} 4 in the formula (C-I) The preferred examples are also the same. Moreover, M < ¹ > is synonymous with M in the said general formula (CI), and its preferable example is also the same.

Specifically, in the general formula (C-II), X ¹¹ , X ¹² , X ¹³ and X ¹⁴ are each independently —SO—Z ¹¹ , —SO ₂ —Z ¹¹ or —SO ₂ NR. ²³ represents R ²⁴ .
Z ¹¹ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group Represents a heterocyclic group.
R ²³ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted group Or an unsubstituted heterocyclic group, and R ²⁴ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, substituted or unsubstituted It represents a substituted aryl group or a substituted or unsubstituted heterocyclic group.
Y ¹¹ , Y ¹² , Y ¹³ , Y ¹⁴ , Y ¹⁵ , Y ¹⁶ , Y ¹⁷ and Y ¹⁸ are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, alkenyl 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, ureido group, sulfamoylamino group, alkylthio group, arylthio group, Alkoxycarbonylamino group, sulfonamido group, carbamoyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonyl group, aryloxycarbonylamino group, imide group, heterocyclic ring A thio group, a phosphoryl group, an acyl group, a carboxyl group, or Represents a sulfo group, each group may further have a substituent.
a ¹¹ ~a ¹⁴ each represent a number of substituents X ¹¹ to X ^14, each independently represents an integer of 0 to 2, never all 0 at the same time. Incidentally, when a ¹¹ ~a ¹⁴ represents 2, two X ¹¹ to X ¹⁴ may each be the same or different.
M ¹ is a hydrogen atom, a metal element or an oxide thereof, a hydroxide, or a halide.

In the general formula (C-II), preferably a ^{11 to} a ¹⁴ each represents an independent integer of 1 or 2 in a range of 4 ≦ a ¹¹ + a ¹² + a ¹³ + a ¹⁴ ≦ 8, and particularly preferably 4 ≦ a ¹¹ + a ¹² + a ¹³ + a ¹⁴ ≦ 6, and particularly preferred is when a ¹¹ = a ¹² = a ¹³ = a ¹⁴ = 1.

  Among the compounds represented by formula (C-II), particularly preferred combinations of substituents are as follows.

As X ^{11 to} X ¹⁴ , —SO ₂ —Z ¹¹ or —SO ₂ NR ²³ R ²⁴ is particularly preferable.

Z ¹¹ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group Is most preferred.

R ²³ is preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a hydrogen atom, a substituted alkyl group, or a substituted aryl group Substituted heterocyclic groups are most preferred.

R ²⁴ is preferably each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a substituted alkyl group, a substituted aryl group, and a substituted heterocyclic group Is most preferred.

Y ^{11 to} Y ¹⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an alkoxy group, an amide group, a ureido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group. Particularly preferred are a hydrogen atom, a halogen atom and a cyano group, and a hydrogen atom is most preferred.

a ^{11 to} a ¹⁴ are preferably each independently 1 or 2, particularly preferably all 1.

M ¹ represents a hydrogen atom, a metal element or oxide thereof, a hydroxide, or a halide, and Cu, Ni, Zn, and Al are particularly preferable, and Cu is most preferable among them.

  Regarding the preferred combination of substituents of the compound represented by the general formula (C-II), a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  The compound represented by the general formula (CI) is inevitably different in the introduction position and introduction number of substituents Rn (n = 1 to 4) and Yq (q = 1 to 4) depending on the synthesis method. In general, it is a body mixture, and these analog mixtures are often represented by a statistical average. The present invention has found that a specific mixture is particularly preferable when these analog mixtures are classified into the following three types.

  In the present invention, the phthalocyanine dye analog mixture, which is a compound represented by the general formulas (CI) and (C-II), is defined by classifying into the following three types based on the substitution position.

(1) β-position substitution type: (phthalocyanine dye having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position)

(2) α-position substitution type: (phthalocyanine dye having a specific substituent at positions 1 and / or 4, 5 and / or 8, 9 and / or 12, 13 and / or 16)

(3) α, β-position mixed substitution type: (phthalocyanine dye having a specific substituent without regularity at positions 1 to 16)

  In the present specification, when a derivative of a phthalocyanine dye having a different structure (especially a substitution position) is described, the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used.

  Examples of the phthalocyanine derivative used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.K. C. Leznoff-A. B. P. Lever co-authored by VCH and published in 'Phthalogicanes-Properties and Applications' (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

The compound represented by the general formula (CI) of the present invention is WO00 / 17275, 0
0/08103, 00/08101, 98/41853, and JP-A-10-36471, for example, sulfonation, sulfonyl chlorideation, amidation reaction of unsubstituted phthalocyanine compounds It can be synthesized via. In this case, sulfonation can occur at any position of the phthalocyanine nucleus, and the number of sulfonation is difficult to control. Therefore, when a sulfo group is introduced under such reaction conditions, the position and number of the sulfo group introduced into the product cannot be specified, and a mixture in which the number of substituents and the substitution position are different is always given. Therefore, when synthesizing the compound of the present invention using it as a raw material, the number and substitution position of the heterocyclic substituted sulfamoyl group cannot be specified, so the compound of the present invention includes several types of compounds having different numbers of substituents and substitution positions. Α, β-position mixed substitution mixture.

  As described above, for example, when a large number of electron-withdrawing groups such as sulfamoyl groups are introduced into the phthalocyanine nucleus, the oxidation potential becomes more noble and ozone resistance increases. According to the above synthesis method, it is inevitable that a small amount of electron-withdrawing groups are introduced, that is, a phthalocyanine dye having a lower oxidation potential is mixed. Therefore, in order to improve ozone resistance, it is more preferable to use a synthesis method that suppresses the formation of a compound having a lower oxidation potential.

  On the other hand, the compound represented by the general formula (C-II) of the present invention includes, for example, a phthalonitrile derivative (compound P) and / or a diiminoisoindoline derivative (compound Q) represented by the following formula: It can derive from the compound obtained by making it react with the metal derivative represented by general formula (C-III).

  In the compounds P and Q, p represents 11 to 14, and q and q 'each independently represents 11 to 18.

Formula (C-III)
M- (Y) _d
In the general formula (C-III), M is synonymous with M in the compounds represented by the general formulas (CI) and (C-II), and Y is a halogen atom, acetate anion, acetylacetate. Represents a monovalent or divalent ligand such as nate or oxygen, and d represents an integer of 1 to 4.

  That is, according to the above synthesis method, a specific number of desired substituents can be introduced. In particular, when a large number of electron withdrawing groups are to be introduced to increase the oxidation potential as in the present invention, the above synthesis method is compared with the synthesis method of the compound represented by the general formula (CI). Very good.

Thus the general formula obtained (C-II) compound represented by the normal, by the following general formula which are isomers with respect to the substitution site of each ^{X p (C-II-1} ) ~ (C-II-4) It is a mixture of the compounds represented, that is, β-position substitution type (phthalocyanine dyes having specific substituents at the 2 and / or 3 position, the 6 and / or 7 position, the 10 and or 11 position, the 14 and or 15 position). ing.

In the general formulas (C-II-1) to (C-II-4), R ^{1 to} R ⁴ are the same as (X ¹¹ ) a ¹¹ to (X ¹⁴ ) a ^{14 in the} general formula (C-II). It is synonymous.

  In the present invention, it has been found that it is very important for improving the robustness that the oxidation potential is higher than 1.0 V (vs SCE) in any substitution type. Among these, the β-position substitution type tends to be superior in hue, light fastness, ozone gas resistance and the like than the α, β-position mixed substitution type.

  Preferable examples of the dye represented by the general formula (CI) or (C-II) include compounds (C-101 to C-120) described in JP-A No. 2003-73598. However, the present invention is not limited to these.

  The compound represented by the general formula (CI) can be synthesized according to the aforementioned patent. The compound represented by the general formula (C-II) is synthesized by the method described in JP-A Nos. 2000-292645, 2001-237090, 2001-243524, and 2001-280387. be able to. Further, the starting material, the dye intermediate and the synthesis route are not limited by these.

    As content in the resin composition of the oil-soluble pigment | dye used for this invention, 0.05-50 mass% is preferable with respect to a resin composition, and 0.1-10 mass% is more preferable.

(Hydrophobic polymer)
Next, the hydrophobic polymer used in the present invention will be described.
The hydrophobic polymer contained in the fine particle dispersion and the resin composition of the present invention is preferably a hydrophobic polymer having a glass transition temperature (Tg) of 40 ° C. or higher, and a high molecular compound with little or no moisture absorption or adsorption is used. The polymer may be a natural polymer or a synthetic polymer, and is preferably a transparent or translucent colorless polymer compound. The structure of the hydrophobic polymer may be a polymer obtained by polycondensation, a polymer obtained from vinyl polymerization, or a polymer obtained by a polymer reaction.

As the hydrophobic polymer used in the present invention, a homopolymer of any monomer selected from the monomer group shown as a specific example below may be used, and a copolymer freely combining any monomers may be used. Also good.
Moreover, there is no restriction | limiting in particular in the monomer unit which can be used, As long as it can superpose | polymerize by a normal radical polymerization method, arbitrary things can be used.

  Further, the polymer obtained by the above polycondensation is preferably a polyester-based polymer, for example, a resin composed of a polyvalent carboxylic acid and a polyhydric alcohol, and a resin obtained by condensation polymerization alone or in combination of two or more monomers. Can be mentioned.

  The polyvalent carboxylic acids are not particularly limited. For example, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenic acid, sulfo Terephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7dicarboxylic acid, 5 [4-sulfophenoxy] isophthalic acid, sulfoterephthalic acid, p-oxybenzoic acid, p- (hydroxyethoxy) ) Benzoic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, hexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, etc. Aromatic polyvalent carboxylic acid, aromatic oxycarboxylic acid, fat shown Family dicarboxylic acids, alicyclic dicarboxylic acids, and the like. These metal salts can also be used as an ammonium salt or the like.

The polyhydric alcohols are not particularly limited. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 2,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolethane, Trimethylolpropane, glycerin, pentaerythritol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, spiroglycol, tricyclodecanediol, tricyclodecane dimethanol, metaxy Aliphatic polyhydric alcohols, alicyclic polyhydric alcohols, aromatic polyhydric alcohols and the like represented by ethylene glycol, orthoxylene glycol, 1,4-phenylene glycol, bisphenol A, lactone polyester, polyols, etc. Can be mentioned.
In addition, the polyester resin polymerized by combining the polyhydric carboxylic acids and the polyhydric alcohols alone or in combination of two or more thereof is a polymer chain terminal using a generally known end-capping compound. What sealed the polar group of can also be used.

The polymer obtained from the vinyl monomer may be a homopolymer of any monomer selected from the monomer group shown as a specific example below, or may be a copolymer in which a plurality of arbitrary monomers are freely combined.
The monomer unit that can be used is not particularly limited, and any monomer unit can be used as long as it can be polymerized by an ordinary radical polymerization method.
Although the specific example of a vinyl monomer is given to the following, this invention is not limited to these at all.

  Examples of the vinyl monomer group include olefins, α, β-unsaturated carboxylic acids and salts thereof, derivatives of α, β-unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids, styrenes, and the like. Examples thereof include derivatives thereof, vinyl ethers, vinyl esters, and other polymerizable monomers.

  Examples of the olefins include ethylene, propylene, isoprene, butadiene, vinyl chloride, vinylidene chloride, 6-hydroxy-1-hexene, cyclopentadiene, 4-pentenoic acid, methyl 8-nonenoate, vinyl sulfonic acid, trimethylvinylsilane, tri Examples include methoxyvinylsilane, butadiene, pentadiene, isoprene, 1,4-divinylcyclohexane, 1,2,5-trivinylcyclohexane, and the like.

  Examples of the α, β-unsaturated carboxylic acid and salts thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, ammonium methacrylate, and potassium itaconate.

  Examples of the α, β-unsaturated carboxylic acid derivatives include alkyl acrylates (eg, methyl acrylate, ethyl acrylate, n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-dodecyl acrylate, etc.), substituted alkyl acrylates (eg, 2-chloroethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, allyl acrylate, etc.), alkyl methacrylate (eg, methyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate, etc.), substituted alkyl methacrylate [eg, 2-hydroxyethyl methacrylate, glycidyl methacrylate, glycerin monomethacrylate, 2-acetoxyethyl methacrylate Chryrate, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (polyoxyethylene addition moles = 2-100), polyethylene glycol monomethacrylate (polyoxyethylene addition moles = 2-2) 100), polypropylene glycol monomethacrylate (added mole number of polyoxypropylene = 2-100), 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl Methacrylates, allyl methacrylates, etc.], derivatives of unsaturated dicarboxylic acids (eg monobutyl maleate, dimethyl maleate, monomethyl itaconate, itacon) Dibutyl etc.), polyfunctional esters (for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, And dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2,4-cyclohexanetetramethacrylate, etc.).

  Examples of the amides of the α, β-unsaturated carboxylic acid include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylacrylamide, N-tertbutylacrylamide, N-tert octyl methacrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloyl morpholine, diacetone acrylamide, itaconic acid diamide, N-methylmaleimide, 2-acrylamide -2-methylpropanesulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine and the like.

  Examples of the styrene and derivatives thereof include styrene, vinyl toluene, p-tertbutyl styrene, vinyl benzoic acid, methyl vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-hydroxymethyl styrene, p- Examples include styrene sulfonic acid sodium salt, p-styrene sulfinic acid potassium salt, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, and the like.

Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, and methoxyethyl vinyl ether.
Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, and the like.
Examples of other polymerizable monomers include N-vinyl pyrrolidone, 2-vinyl oxazoline, 2-isopropenyl oxazoline, divinyl sulfone and the like.

  Among the hydrophobic polymers of the present invention synthesized by copolymerization combining the above monomers, the main component is a single polymer such as acrylamide, methacrylamide, acrylic ester, methacrylic ester, styrene, vinyl ester, vinyl ether, olefin, etc. Those composed of a polymer or a copolymer are preferably selected.

  The hydrophobic polymer contained in the fine particle dispersion and the resin composition of the present invention has a glass transition temperature (Tg) of 40 ° C. or more in order to eliminate nozzle clogging in ink jet printing and improve and improve ink discharge performance. Is preferred. The glass transition temperature (Tg) is more preferably a hydrophobic polymer of 45 ° C. or higher, and most preferably a hydrophobic polymer having a Tg of 50 ° C. or higher. Although there is no restriction | limiting in particular in the upper limit of this glass transition temperature (Tg), about 180 degreeC is enough with the normal ink for inkjet printing.

In the present specification, the glass transition temperature (Tg) in the case of a copolymer is calculated according to the following formula.
1 / Tg = Σ (x _i / Tg _i )
In the above formula, it is assumed that n monomer units from i = 1 to n are copolymerized in the copolymer polymer. x _i is the mass fraction of the i-th monomer (Σx _i = 1), Tg _i is the glass transition temperature (absolute temperature display) of the homopolymer of the i-th monomer, and Σ is from i = 1 to n Take the sum. The value (Tg _i ) of the glass transition temperature of the homopolymer of each monomer is, for example, J. Brandrup, E .; H. Values described in “Polymer Handbook” (3rd Edition, Wiley-Interscience, 1989) by Immergut can be employed.

  In the present invention, two or more hydrophobic polymers may be used in combination as required. When two or more polymers having different glass transition temperatures are blended and used, it is preferable that the mass average Tg falls within the above-described 40 ° C. or higher.

  The hydrophobic polymer of the present invention is preferably a hydrophobic polymer that can be dispersed in an aqueous solvent. Examples of the dispersed state include latex in which fine particles of water-insoluble hydrophobic polymer are dispersed and polymer molecules dispersed in a molecular state or a micelle form. Is preferred. The average particle diameter of the dispersed particles is 1 to 50000 nm, preferably 5 to 1000 nm, more preferably 10 to 500 nm, and particularly preferably 50 to 200 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution. It is also preferable to use a mixture of two or more types having a monodisperse particle size distribution in order to control the properties of the resin composition liquid.

  Preferable specific examples of the hydrophobic polymer dispersible in the aqueous medium include acrylic polymers, polyesters, rubbers (for example, SBR rubber), polyurethanes, polyvinyl chlorides, polyvinyl acetates, polyvinylidene chlorides, Hydrophobic polymers such as polyolefins can be suitably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by copolymerizing two or more monomers. . In the case of a copolymer, it may be a random copolymer, a block copolymer, or a graft copolymer. The molecular weight of these polymers is preferably 5,000 to 1,000,000 in terms of number average molecular weight, and more preferably 10,000 to 200,000. When the molecular weight is too smaller than the above range, the mechanical strength of the emulsion layer may be insufficient. On the other hand, when the molecular weight is too large, the film formability may be poor. A crosslinkable polymer latex is particularly preferably used.

The aqueous solvent in which the hydrophobic polymer is soluble or dispersible is obtained by mixing water or water with 70% by mass or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolves such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide.
Even in the case of a system in which the hydrophobic polymer is not completely dissolved thermodynamically and exists in a so-called dispersed state, the term aqueous solvent is used in this specification.

Specific examples of the hydrophobic polymer used in the present invention and the glass transition temperature (Tg) thereof are listed below, but the present invention is not limited to these.
(P-1) Poly (4-biphenyl acrylate) Tg = 110 ° C.
(P-2) Poly (t-butyl acrylate) Tg = 107 ° C.
(P-3) Poly (2-chloroacrylate) Tg = 53 ° C.
(P-4) Poly (2-naphthyl acrylate) Tg = 85 ° C.
(P-5) Poly (acrylamide) Tg = 165 ° C.
(P-6) Poly (N-butylacrylamide) Tg = 46 ° C.
(P-7) Poly (Nt-butylacrylamide) Tg = 128 ° C.
(P-8) Poly (benzyl methacrylate) Tg = 54 ° C.
(P-9) Poly (t-butyl methacrylate) Tg = 118 ° C.
(P-10) Poly (4-t-butylcyclohexyl methacrylate) Tg = 83 ° C.
(P-11) Poly (ethyl methacrylate) Tg = 65 ° C.
(P-12) Poly (iso-propyl methacrylate) Tg = 81 ° C.
(P-13) Poly (methyl methacrylate) Tg = 105 ° C.
(P-14) Poly (phenyl methacrylate) Tg = 110 ° C.
(P-15) Poly (styrene) Tg = 100 ° C
(P-16) Poly (2-ethylstyrene) Tg = 103 ° C.
(P-17) Poly (2-ethoxymethylstyrene) Tg = 74 ° C.
(P-18) Poly [4- (1-hydroxy-1-methylbutyl) styrene]]
Tg = 130 ° C
(P-19) Poly (2-methylstyrene) Tg = 136 ° C.
(P-20) Poly (4-propoxystyrene) Tg = 70 ° C.
(P-21) Poly (4-acetylstyrene) Tg = 116 ° C.
And the copolymer which consists of arbitrary combinations of the structural unit (monomer) of the said polymer.

The said hydrophobic polymer may be used individually by 1 type, and may use 2 or more types together as needed.
The amount of the hydrophobic polymer used for the preparation of the fine particles of the present invention is preferably 10 to 500% by mass, and more preferably 20 to 300% by mass, with respect to the dye that coexists in the fine particles.

(High boiling point organic solvent)
The fine particle dispersion containing the oil-soluble compound and the hydrophobic polymer of the present invention described above preferably contains a high boiling point organic solvent in order to form fine particles having excellent hue and stability.
The fine particle dispersion of the present invention contains at least an oil-soluble compound and a hydrophobic polymer, preferably also contains a high-boiling organic solvent, and if necessary, has a boiling point of 200 ° C. or lower and solubility in water. It is preferable to prepare by removing the auxiliary solvent when the auxiliary solvent is used after mixing and emulsifying and dispersing the solution containing the auxiliary solvent having a weight of 25 g or less and the aqueous medium.

In the present invention, the high-boiling organic solvent is an organic solvent having a boiling point of 200 ° C. or higher and a melting point of 80 ° C. or lower, and particularly preferably has a water solubility of 4 g or lower at 25 ° C. If the water solubility (25 ° C.) exceeds 4 g, the fine particles constituting the resin composition are likely to have an enlarged particle size or agglomerate over time, which may have a serious adverse effect on the ink ejection performance. There is. The solubility of the water is preferably 4 g or less, more preferably 3 g or less, particularly preferably 2 g or less, and most preferably 1 g or less.
In the present specification, the above-mentioned “water solubility” is the saturation concentration of water in a high boiling point organic solvent at 25 ° C., and means the mass (g) of water that can be dissolved in 100 g of the high boiling point organic solvent at 25 ° C. To do.

  In the present invention, the amount of the high-boiling organic solvent used is preferably 5 to 200% by mass and more preferably 10 to 100% by mass with respect to the pigment in which fine particles coexist.

  In the present invention, the high-boiling organic solvent is preferably a compound represented by the following formulas [S-1] to [S-9].

In the above formula [S-1], R ₁ , R ₂ and R ₃ each independently represents an aliphatic group or an aryl group. A, b and c each independently represents 0 or 1;

In the formula [S-2], R ₄ and R ₅ each independently represents an aliphatic group or an aryl group, and R ₆ represents a halogen atom (F, Cl, Br, I and so on), an alkyl group, an alkoxy group. Represents an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and d represents an integer of 0 to 3. When d is plural, plural R ₆ may be the same or different.

In the formula [S-3], Ar represents an aryl group, e represents an integer of 1 to 6, and R ₇ represents an e-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In the formula [S-4], R ₈ represents an aliphatic group, f represents an integer of 1 to 6, and R ₉ represents an f-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond.

In the formula [S-5], g represents an integer of 2 to 6, R ₁₀ represents a g-valent hydrocarbon group (excluding an aryl group), and R ₁₁ represents an aliphatic group or an aryl group.

In the formula [S-6], R ₁₂ , R ₁₃ and R ₁₄ each independently represents a hydrogen atom, an aliphatic group or an aryl group. X represents —CO— or —SO ₂ —. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄ may be bonded to each other to form a ring.

In the formula [S-7], R ₁₅ represents an aliphatic group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an aryl group or a cyano group, R ₁₆ represents a halogen atom, an aliphatic group, An aryl group, an alkoxy group or an aryloxy group is represented, and h represents an integer of 0 to 3. When h is plural, plural R ₁₆ may be the same or different.

In the formula [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic group or an aryl group, R ₁₉ represents a halogen atom, an aliphatic group, an aryl group, an alkoxy group or an aryloxy group, and i Represents an integer of 0-4. When i is plural, plural R ₁₉ may be the same or different.

In the formula [S-9], R ₂₀ and R ₂₁ represent an aliphatic group or an aryl group. j represents 1 or 2;

In the formulas [S-1] to [S-9], when R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are an aliphatic group or a group having an aliphatic group, the aliphatic group is linear. These may be branched or cyclic, and may contain an unsaturated bond or may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group.

In the formulas [S-1] to [S-9], R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are cyclic aliphatic groups, that is, cycloalkyl groups, or groups having a cycloalkyl group. In some cases, the cycloalkyl group may have an unsaturated bond in a 3- to 8-membered ring, and may have a substituent or a bridging group. Examples of the substituent include a halogen atom, an aliphatic group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, and an alkyl group, and examples of the cross-linking group include methylene, ethylene, isopropylidene, and the like.

In the formulas [S-1] to [S-9], when R _{1 to} R ₆ , R ₈ and R _{11 to} R ₂₁ are an aryl group or a group having an aryl group, the aryl group is a halogen atom or an aliphatic group. , An aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group and the like may be substituted.

In the formulas [S-3], [S-4], and [S-5], when R ₇ , R _9, or R ₁₀ is a hydrocarbon group, the hydrocarbon group is a cyclic structure (for example, a benzene ring or a cyclopentane ring). , A cyclohexane ring) or an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

Hereinafter, among the high boiling point organic solvents represented by the formulas [S-1] to [S-9], particularly preferred high boiling point organic solvents will be described.
In the formula [S-1], R ₁ , R ₂ and R ₃ are each independently an aliphatic group having 1 to 24 (preferably 4 to 18) carbon atoms (hereinafter abbreviated as C number) (for example, n-butyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, oleyl, 2-chloroethyl, 2,3-dichloropropyl, 2-butoxyethyl, 2-phenoxyethyl, Cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 4-methylcyclohexyl) or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, phenyl, cresyl, p-nonylphenyl, xylyl, cumenyl, p -Methoxyphenyl, p-methoxycarbonylphenyl). a, b, and c are each independently 0 or 1, and more preferably, all of a, b, and c are 1.

In the formula [S-2], R ₄ and R ₅ are each an aliphatic group having 1 to 24 carbon atoms (preferably 4 to 18) (for example, the same group as the alkyl group described above for R ₁ , ethoxycarbonylmethyl, 1 , 1-diethylpropyl, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1,5-dimethylhexyl, 3,5,5-trimethylcyclohexyl, menthyl, bornyl, 1-methylcyclohexyl) or C number 6 to 24 (preferably 6 to 18) aryl groups (for example, the aryl groups mentioned for R ₁ , 4-t-butylphenyl, 4-t-octylphenyl, 1,3,5-trimethylphenyl, 2, 4,6-di-t-butylphenyl, 2,4, -di-t-pentylphenyl), R ₆ is a halogen atom (preferably a chlorine atom), and C 1-18 Alkyl group (for example, methyl, isopropyl, t-butyl, n-dodecyl), C 1-18 alkoxy group (for example, methoxy, n-butoxy, n-octyloxy, methoxyethoxy, benzyloxy), C number 6 -18 aryloxy groups (for example, phenoxy, p-tolyloxy, 4-methoxyphenoxy, 4-t-butylphenoxy) or C2-C19 alkoxycarbonyl groups (for example, methoxycarbonyl, n-butoxycarbonyl, 2- Ethylhexyloxycarbonyl) or an aryloxycarbonyl group having 6 to 25 carbon atoms, and d is 0 or 1.

In the formula [S-3], Ar is an aryl group having 6 to 24 carbon atoms (preferably 6 to 18), such as phenyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, 4-n-butoxyphenyl, 1,3,5-trimethylphenyl), e is an integer of 1 to 4 (preferably 1 to 3), and R ₇ is an e-valent C 2-24 hydrocarbon (preferably 2-18) hydrocarbon. group [for example, alkyl groups as described as R _4, a cycloalkyl group, an aryl _{group, - (CH 2) 2 -} ,

である。 Or an e-valent hydrocarbon group having 4 to 24 (preferably 4 to 18) carbon atoms bonded to each other via an ether bond [for example, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ (OCH ₂ CH _{2) 3 -, - CH 2} CH 2 CH 2 OCH 2 CH 2 CH 2 -,

It is.

In the formula [S-4], R ₈ is an aliphatic group having 1 to 24 carbon atoms (preferably 1 to 17) (for example, methyl, n-propyl, 1-hydroxyethyl, 1-ethylpentyl, n-undecyl, Pentadecyl, 8,9-epoxyheptadecyl, cyclopropyl, cyclohexyl, 4-methylcyclohexyl), f is an integer of 1 to 4 (preferably 1 to 3), and R ₉ is an F-valent C number of 2 to 2. 24 (preferably 2 to 18) hydrocarbon groups or hydrocarbon groups connected to each other by an ether bond having 4 to 24 carbon atoms (preferably 4 to 18 carbon atoms) having a valence of c (for example, the groups mentioned for R ₇ above) It is.

In the formula [S-5], g is 2 to 4 (preferably 2 or 3), and R ₁₀ is a g-valent hydrocarbon group [for example, —CH ₂ —, — (CH ₂ ) ₂ —, — ( _{CH 2) 4 -, - (} CH 2) 7 -,

R ₁₁ represents an aliphatic group having 1 to 24 carbon atoms (preferably 4 to 18) or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, the aliphatic groups mentioned for R ₄ above). An aryl group).

In the formula [S-6], R ₁₂ is a hydrogen atom, an aliphatic group having 1 to 24 carbon atoms (preferably 3 to 20) [for example, n-propyl, 1-ethylpentyl, n-undecyl, n-pentadecyl, 2,4-di-t-pentylphenoxymethyl, 4-t-octylphenoxymethyl, 3- (2,4-di-t-butylphenoxy) propyl, 1- (2,4-di-t-butylphenoxy) propyl Cyclohexyl, 4-methylcyclohexyl), or an aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, the aryl group mentioned for Ar), R ₁₃ and R ₁₄ are each a hydrogen atom, C ₁₄ An aliphatic group having a number of 1 to 24 (preferably 1 to 18) (for example, methyl, ethyl, isopropyl, n-butyl, n-hexyl, 2-ethylhexyl, n-dodecyl, cyclopentyl, Black propyl), or C number 6-18 (preferably an aryl group having from 6 to 15) (e.g., phenyl, 1-naphthyl, p- tolyl). R ₁₃ and R ₁₄ may be bonded to each other to form a pyrrolidine ring, piperidine ring, or morpholine ring together with N, or R ₁₂ and R ₁₃ may be bonded to each other to form a pyrrolidone ring. X is —CO— or —SO ₂ —, and preferably X is —CO—.

In the formula [S-7], R ₁₅ is an aliphatic group having 1 to 24 carbon atoms (preferably 3 to 18) (for example, methyl, isopropyl, t-butyl, t-pentyl, t-hexyl, t-octyl, 2-butyl, 2-hexyl, 2-octyl, 2-dodecyl, 2-hexadecyl, t-pentadecyl, cyclopentyl, cyclohexyl), an alkoxycarbonyl group having 2 to 24 carbon atoms (preferably 5 to 17) (for example, n- Butoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl) C 1-24 (preferably 1-18) alkylsulfonyl group (eg, methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl), C number 6-30 (preferably 6-24) arylsulfonyl groups (eg, p-tolylsulfonyl, p-dodo) Sill phenylsulfonyl, p- hexadecyloxy phenylsulfonyl), an aryl group (e.g., a C number of 6 to 32 (preferably 6 to 24), phenyl, p- tolyl) or a cyano group, R ₁₆ is a halogen atom (preferably is Cl), an alkyl group (e.g., a C number of 1 to 24 (preferably 1 to 18), wherein the alkyl group described for R _15), C the number cycloalkyl group having 3 to 18 (preferably 5 to 17) (e.g. , Cyclopentyl, cyclohexyl), C 6-32 (preferably 6-24) aryl group (eg, phenyl, p-tolyl) C 1-24 (preferably 1-18) alkoxy group (eg, methoxy, n-butoxy, 2-ethylhexyloxy, benzyloxy, n-dodecyloxy, n-hexadecyloxy), or C 6-32 (preferably Is an aryloxy group (for example, phenoxy, pt-butylphenoxy, pt-octylphenoxy, m-pentadecylphenoxy, p-dodecyloxyphenoxy), and h is an integer of 1 to 2 It is.

In the formula [S-8], R ₁₇ and R ₁₈ are the same as R ₁₃ and R ₁₄ , and R ₁₉ is the same as R ₁₆ .

In the formula [S-9], R ₂₀ and R ₂₁ are the same as R ₁ , R ₂ and R ₃ . j represents 1 or 2, and preferably j is 1.

  Specific examples of the high boiling point organic solvent used in the present invention include compounds (S-1 to S-93) described in JP-A-2003-73598, but the present invention is limited to these. It is not a thing.

  In the present invention, the high boiling point organic solvent may be used alone or in combination of two or more [for example, tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl) sebacate, dibutyl phthalate and Poly (Nt-butylacrylamide)] may be used.

  In the present invention, the mass ratio of the oil-soluble compound and the high-boiling organic solvent is preferably such that oil-soluble compound: high-boiling organic solvent is 1: 0.01 to 1: 1, and 1: 0. More preferably, it is from 05 to 1: 0.5.

  Examples of other high boiling point organic solvents used in the present invention and / or methods for synthesizing these high boiling point organic solvents include, for example, US Pat. Nos. 2,322,027 and 2,533,514. 2,772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3, 700,454, 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4,004,928, 4,080,209, 4,127,413, 4,193,802, 4,207,393, 4,220 No.711, No.4,239,851, No.4,278,75 No. 4,353,979, No. 4,363,873, No. 4,430,421, No. 4,430,422, No. 4,464,464, No. 4 No. 4,483,918, No. 4,540,657, No. 4,684,606, No. 4,728,599, No. 4,745,049, No. 4,935,321. 5,013,639, European Patent Nos. 276,319A, 286,253A, 289,820A, 309,158A, 309,159A, 309, No. 160A, No. 509,311A, No. 510,576A, East German Patent Nos. 147,009, No. 157,147, No. 159,573, No. 225,240A, British Patent No. 2 , 091,124A, etc. 47335, 50-26530, 51-25133, 51-26036, 51-27921, 51-27922, 51-149028, 52-46816, 53-1520 53-1521, 53-15127, 53-146622, 54-91325, 54-106228, 54-118246, 55-59464, 56-64333, 56-81836, 59-204041, 61-84441, 62-118345, 62-247364, 63-167357, 63-214744, 63-301941, 64 -9452, 64-9454, 64-68745, JP-A-1-101543, 1-102454 No. 2-792, No. 2-4239, No. 2-43541, No. 4-29237, No. 4-30165, No. 4-232946, No. 4-346338, etc. ing.

(Co-solvent)
In the resin composition of this invention, an auxiliary | assistant solvent can be used with the above-mentioned high boiling point organic solvent as needed. This auxiliary solvent is a low-boiling solvent or a water-soluble organic solvent, and is a solvent that is removed by evaporation, membrane dialysis, ultrafiltration, or the like after emulsification and dispersion of an organic solvent phase containing a dye.
In the case of preparing fine particles containing at least an oil-soluble compound, a hydrophobic polymer, and a high-boiling organic solvent according to the present invention, in order to obtain a stable dispersion having a narrow particle size distribution, It is preferable that the solubility in is small. On the other hand, in order to facilitate removal of the auxiliary solvent after emulsification and dispersion, solubility in water is required to some extent. Therefore, a solvent that is completely soluble in water, such as methanol, ethanol, isopropyl alcohol, and acetone, is not preferable for obtaining a stable dispersion having a narrow particle size distribution.
In the present invention, the solubility of the auxiliary solvent in water (25 ° C., with respect to 100 g of water) is preferably 0.5 to 25 g, more preferably 1 g to 20 g.
Preferred specific examples (AS-1 to 11) of the auxiliary solvent and their solubility in water are shown below, but the present invention is not limited thereto.

Auxiliary solvent Solubility in water (25 ℃)
(AS-1) 8 g of ethyl acetate
(AS-2) Propyl acetate 2g
(AS-3) 2-ethylbutyl acetate <1 g
(AS-4) 2-ethylene acetate 20g
(AS-5) 2-Ethoxyethyl acetate 25 g
(AS-6) Butyl acetate 2g
(AS-7) 2 g of ethyl propionate
(AS-8) Acetylacetone 12g
(AS-9) Ethyl acetoacetate 12g
(AS-10) 2- (2-n-butoxyethoxy) ethyl acetate 2 g
(AS-11) Cyclohexanone 15 g

  In the present invention, the amount of the auxiliary solvent to be used is preferably 1 to 200 times, more preferably 2 to 100 times the amount of the coexisting pigment in the fine particles.

(Preparation of resin composition)
The above-mentioned oil-soluble compound is used for the colorant of the resin composition of the present invention, and these dyes are preferably used in a proportion of about 0.1 to 30% by mass in the resin composition.
The resin composition of the present invention can be prepared, for example, as follows. (1) a solution containing the oil-soluble compound, the hydrophobic polymer, and, if necessary, the high-boiling organic solvent and the auxiliary solvent (hereinafter sometimes referred to as “oil phase”), and (2) heat. The water-soluble vinyl resin having crosslinkability is mixed with an aqueous medium (hereinafter sometimes referred to as “aqueous phase”) and emulsified and dispersed, and then the auxiliary solvent is removed to obtain the intended book. The resin composition of the invention can be obtained. Here, the water-soluble resin having thermal crosslinkability (2) or a part thereof may be added in advance to the aqueous phase, or added after emulsifying and dispersing an oil-soluble compound or the like. Also good.
In the following description, the resin composition of the present invention used for the ink jet printing method may be referred to as “ink composition” or simply “ink”.

  It is desirable to use ion-exchanged water (deionized water) instead of general water containing various ions. Moreover, a water-soluble organic solvent can be used as needed. The water-soluble organic solvent may be any water-soluble organic solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol. Alkyl alcohols having 1 to 4 carbon atoms such as amides such as dimethylformamide and dimethylacetamide; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethylene glycol, polypropylene glycol and the like Polyalkylene glycols; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol Alkylene glycols containing 2 to 6 carbon atoms such as diol, diethylene glycol, etc .; glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Lower alkyl ethers of polyhydric alcohols such as butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2 -Imidazoline etc. are mentioned. Among these water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers such as triethylene glycol monomethyl ether are preferable.

  In the ink (resin composition) according to the present invention, a surfactant, a wetting agent, an emulsion stabilizer, a dye stabilizer, a preservative, Various additives such as antifungal agents can be added as necessary.

  Examples of the surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate esters, naphthalene sulfonate formalin condensates, polyoxyethylene alkyls. Anionic surfactants such as sulfate salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid Nonionic surfactants such as esters and oxyethyleneoxypropylene block copolymers, and acetylene-based polyoxyethylene oxide surfactants. URFYNOLS "(manufactured by Air Products & Chemicals), amine oxide type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxide, and JP-A-59-157636 (37) to (38), Research Disclosure No. The thing of 308119 (1989) is also mentioned suitably.

  In the present invention, a water-soluble polymer can be added together with these surfactants for the purpose of stabilization immediately after emulsification. Examples of the water-soluble polymer include polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, polyacrylic acid, polyacrylamide and copolymers thereof, or natural water-soluble polymers such as polysaccharides, casein, and gelatin.

  When preparing a resin composition containing fine particles (dye) by emulsification and dispersion, it is particularly important to control the particle size of the fine particles in order to improve printing performance. The average particle diameter of the fine particles can be easily measured by a known method. For example, it is diluted with distilled water so that the dye concentration in the resin composition is 0.1 to 1% by mass, and is commercially available. It can be easily measured with a volume average particle diameter measuring machine. Examples of the measuring apparatus include “Microtrac UPA” manufactured by Nikkiso Co., Ltd., and particle size distribution measuring apparatus “LB-500” manufactured by Horiba Seisakusho Co., Ltd.

As the particle diameter of the fine particles contained in the resin composition of the present invention, those having a volume average particle diameter of 0.01 to 0.5 μm are preferable from the viewpoint of obtaining good printing characteristics and ejection performance. The diameter is more preferably from 0.01 to 0.3 μm, particularly preferably from 0.01 to 0.2 μm.
The specific gravity of the fine particles according to the present invention is preferably 0.90 to 1.20, more preferably 0.93 to 1.10, and particularly preferably 0.95 to 1.05. If the specific gravity is out of this range, the emulsification / dispersion work may become difficult, or it may be difficult to exist stably in an aqueous phase system.
The specific gravity of the fine particles is determined by preparing a solution comprising the components of the fine particles and then removing the auxiliary solvent. For example, P79 to P82 of “New Experimental Chemistry Course Volume 1” (Maruzen Co., Ltd.). It can be measured by the method described in 1. and its application.

  In the resin composition of the present invention, the presence of coarse particles greatly affects printing performance. In other words, the coarse particles clog the nozzles of the head, or even if they do not clog, the ink (resin composition) causes non-ejection and ejection pulsation, which has an adverse effect on printing performance that cannot be overlooked. Sometimes. In order to prevent this, when the resin composition of the present invention is used for ink jet printing, it is desirable to suppress 10 particles of 5 μm or more to 1000 particles or less of 1 μm or more in 1 μL of ink.

As a method for removing these coarse particles, a known centrifugal separation method, microfiltration method, or the like can be used. These separation means may be performed immediately after the emulsification dispersion, or may be performed immediately before filling the ink cartridge after various additives such as a wetting agent and a surfactant are added to the emulsification dispersion.
As an effective means for reducing the average particle size of the fine particles in the resin composition and reducing the coarse particles, an emulsifying and dispersing device with mechanical stirring can be suitably used.

  As the above emulsifying and dispersing apparatus, a known apparatus such as a simple stirrer or impeller stirring system, an in-line stirring system, a mill system such as a colloid mill, or an ultrasonic wave application system can be used. Among them, a high-pressure homogenizer is particularly preferable.

The above high-pressure homogenizer is described in detail in US Pat. No. 4,533,254, JP-A-6-47264, etc., but as a commercially available apparatus, “Gorin homogenizer” (APV GAULIN) INC.), “Microfluidizer” (manufactured by MICROFLUIDEX INC.), “Ultimizer” (manufactured by Sugino Machine Co., Ltd.) and the like are known.
In recent years, a high-pressure homogenizer having a mechanism for atomizing in an ultrahigh-pressure jet stream as described in US Pat. No. 5,720,551 is particularly effective for emulsifying and dispersing fine particles according to the present invention. An example of an emulsifying and dispersing apparatus using this ultra-high pressure jet flow is “DeBEE2000” (manufactured by BEE INTERNIONAL LTD.).

The pressure when emulsifying and dispersing using the high-pressure emulsifying disperser is preferably 50 MPa or more (500 bar or more), more preferably 60 MPa or more (600 bar or more), and particularly preferably 180 MPa or more (1800 bar or more).
In the present invention, at the time of emulsification and dispersion, for example, after emulsifying with a stirrer, it is more preferable to use two or more types of emulsifiers together by a method such as passing through a high-pressure homogenizer. In addition, a method of once passing through a high-pressure homogenizer in the step of once emulsifying and dispersing with these emulsifying apparatuses and then adding an additive such as a wetting agent or a surfactant and then filling the cartridge with the resin composition is also preferable.

In the emulsification dispersion of the resin composition of the present invention, when an auxiliary solvent is used in addition to the high boiling point organic solvent, the auxiliary solvent is substantially used from the viewpoint of stability of the obtained emulsion (fine particles) and environmental hygiene. It is preferable to remove completely.
As a method for substantially completely removing the auxiliary solvent, various known methods such as an evaporation method, a vacuum evaporation method, an ultrafiltration method, and the like can be employed depending on the type of the auxiliary solvent. It is efficient and preferable that the auxiliary solvent removing step is performed as soon as possible immediately after emulsification.

  The resin composition of the present invention can contain other components appropriately selected as necessary in addition to the components described above. Other components include, for example, drying inhibitors, penetration enhancers, ultraviolet absorbers, antioxidants, antifungal agents, pH regulators, surface tension regulators, antifoaming agents, viscosity modifiers, dispersants, and dispersion stabilizers. Known additives such as an agent, a rust preventive agent, and a chelating agent.

The anti-drying agent is used for the purpose of preventing clogging due to drying of the ink at the ink ejection port of the nozzle used in the ink jet printing method.
Such a drying inhibitor is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples of the drying inhibitor include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithioglycol, 2-methyl-1,3-propanediol, 1,2,3-hexatriol, and acetylene glycol. Derivatives, polyhydric alcohols typified by glycerin, trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolene, diacetone alcohol Le, polyfunctional compounds such as diethanolamine, etc. urea derivatives Ageraru. Of these, polyhydric alcohols such as glycerin diethylene glycol are particularly preferred.
The said anti-drying agent may be used individually by 1 type, and may use 2 or more types together. These drying inhibitors are preferably contained in the ink composition in an amount of 10 to 50 parts by mass.

  Examples of the penetration accelerator include ethanol, isopropanol, butanol, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, 1,2-hexanediol, etc., in order to obtain ink ejection stability from the ejection head of the inkjet printing apparatus. Alcohols, sodium lauryl sulfate, sodium oleate, and nonionic surfactants listed as the surfactant for emulsification and dispersion. These are effective when added in an amount of 10 to 30% by mass in the resin composition, and are added within a range that does not cause printing bleeding or paper loss (print-through).

  The ultraviolet absorber is used for the purpose of improving image storage stability. For example, JP-A Nos. 58-185677, 61-190537, JP-A-2-782, and JP-A-5-97075. Benzotriazole compounds described in JP-A-9-34057, etc., benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc. Cinnamic acid compounds described in JP-B-48-30492, JP-A-56-21141, JP-A-10-88106, etc., JP-A-4-298503, JP-A-8-53427, JP-A-8- No. 239368, 10-182621, JP-A-8-501291, etc. Closure No. Examples thereof include compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, and so-called fluorescent brighteners.

The antioxidant is used for the purpose of improving the storage stability of the image, and examples thereof include various organic and metal complex anti-fading agents.
Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles. .
Examples of the metal complex anti-fading agent include nickel complexes and zinc complexes. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. Preferred examples include the compounds described in the patent cited in No. 15162 and the compounds represented by the general formulas and compound examples of the representative compounds described on pages 127 to 137 of JP-A-62-215272.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. . These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  Examples of the pH adjuster include inorganic hydroxides such as alkali metal hydroxides such as lithium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate, potassium acetate, sodium silicate, and disodium phosphate. Examples include bases, organic bases such as N-methyldiethanolamine and triethanolamine.

  Examples of the surface tension adjusting agent include nonionic, cationic or anionic surfactants. For example, the surfactant used for the above emulsification dispersion can be used, and the surfactant used here preferably has a solubility in water at 25 ° C. of 0.5% or more.

Preferred examples of the dispersant and dispersion stabilizer include the above-mentioned cations, anions, and nonionic surfactants.
Examples of the antifoaming agent include fluorinated, silicone based compounds and chelating agents represented by EDTA.

In preparing a resin composition containing fine particles by emulsification and dispersion, it is important to control the viscosity and the surface tension in order to ensure good dischargeability. The viscosity of this resin composition can be easily measured by a known method using a commercially available viscometer. An example of such a measuring instrument is a B-type viscometer manufactured by Tokyo Keiki Co., Ltd.
The viscosity of the resin composition of the present invention is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less, in order to ensure good dischargeability.
The surface tension of the resin composition can be easily measured by a known method using a commercially available surface tension meter. An example of such a measuring instrument is a plate type surface tension meter “CBVP-A3” manufactured by Kyowa Interface Science Co., Ltd. The surface tension of the resin composition of the present invention is preferably 20 to 55 mN / m, more preferably 25 to 45 mN / m, in order to ensure good print quality.
Furthermore, as pH of the resin composition of this invention, 6-10 are preferable from a viewpoint of an improvement of storage stability, and 7-10 are more preferable.
The resin composition of this invention turns into an ink composition which can be used conveniently for an inkjet printing system.

(Color filter substrate and manufacturing method)
Next, a color filter substrate produced using the ink (resin composition) described above and a method for producing the same will be described.
FIG. 1 is a cross-sectional view of a color filter substrate showing one embodiment of the present invention. A black matrix (2) is provided in a lattice pattern on a light-transmitting substrate (1) such as a glass substrate, a plastic substrate, or a film substrate, and the ink (resin composition) of the present invention is inkjet printed at the opening of the black matrix. The pixel (3) is formed by heating and curing. Here, if necessary, a protective layer (4) is provided on the upper side, and a transparent electrode layer (5) is further formed on the upper side.

  The method for producing a color filter substrate of the present invention includes (1) a step of providing a pixel layer on a transparent substrate by ink jet printing using the ink (resin composition) described above, and (2) curing the pixel layer by heat treatment. Including a step of causing the step to occur. The color filter substrate of the present invention can be produced, for example, by the procedure as shown in FIGS. That is,

(A) Black matrix formation process First, a black matrix (2) is formed on a translucent substrate (1). Thereby, the recessed part for pixels (6) which provides the above-mentioned ink (resin composition) to the opening part of a black matrix (2) is formed. The black matrix can be formed by a known photolithography method using a resist containing a black pigment or a black dye. At this time, the thickness of the black resist is preferably 0.5 μm or more. When the thickness is less than 0.5 μm, the optical density as the black matrix is lowered, and the shielding function as the black matrix may not be sufficiently achieved. In addition, when a colored ink composition is ejected in the next step, the ink may overflow from the pixel recess (6) and the compositions of different colors adjacent to each other may mix.

(B) Pixel formation step Next, R, G, and B inks (7) are ejected from the jet nozzle (9) of the inkjet printing apparatus (8) toward the substrate so as to fill the pixel recesses (6). Then, each color pixel pattern is formed. At this time, it is preferable to apply the inks so that the respective color inks are not mixed on the black matrix (2).
The ink jet method used in this pixel forming process can be a bubble jet (R) type using an electrothermal transducer as an energy generating element or a piezo jet type using a piezoelectric element. The discharge pattern can be set arbitrarily.

  Next, the ejected ink (7) is cured by heat treatment to form the pixel (3). In the present invention, the above heat treatment should be performed at a high temperature of 150 ° C. or higher in order to sufficiently develop heat resistance, water resistance, solvent resistance, etc., and to make a color filter substrate that can withstand heat treatment and solvent in the subsequent steps. Is desirable.

(C) Protective film formation process Furthermore, a protective film (4) is formed on a pixel (3) as needed. As the protective film (4), a resin material that can be cured by light irradiation or heat treatment, or both, or an inorganic film formed by vapor deposition and sputtering, can be used. Any material may be used as long as it has transparency and has resistance to a subsequent transparent electrode formation process, alignment film formation process, and the like.

  As the resin material for the protective film, for example, an acrylic resin, an epoxy resin, a polyimide resin, or the like is preferably used, but is not limited thereto. In addition, as a method for applying these resin materials, methods such as spin coating, roll coating, bar coating, spray coating, dip coating, and the like can be suitably used, but are not limited thereto.

(D) Transparent electrode layer formation process Then, a transparent electrode layer (5) is formed. As a material for forming the transparent electrode layer (5), metal oxides such as indium-tin oxide, zinc oxide, and titanium oxide when used as a color filter substrate can be suitably used. As a forming method thereof, a known film forming method such as a sputtering method or a vapor deposition method can be used. The color filter substrate of the present invention is produced as described above.

In the production of the color filter substrate of the present invention, the ink jet printing method to be used is not particularly limited, and is a known method, for example, a charge control method for ejecting ink using electrostatic attraction, and vibration of a piezo element. Drop-on-demand method (pressure pulse method) that uses pressure, acoustic ink jet method that changes the electrical signal into an acoustic beam, irradiates the ink and uses the radiation pressure to eject the ink, and heats the ink to form bubbles Any one of the thermal ink jet method using the generated pressure may be used.
Here, the inkjet printing method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving the image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless. A method using transparent ink is also included.

  Examples of the present invention will be described below, but the present invention is not limited to these examples. In this example, “parts” and “%” represent “parts by mass” and “% by mass” unless otherwise specified.

[Example 1]
(Preparation of fine particle dispersion)
20 parts of ethyl acetate, 1.0 part of the following oil-soluble compound (a), 3.0 parts of a hydrophobic polymer (P-2; poly (t-butyl acrylate), Tg = 107 ° C.), and 0 of the following high boiling point organic solvent .5 parts of a mixed solution was prepared. Separately, a mixed solution of 25 parts of water and 0.5 part of sodium di (2-ethylhexyl) sulfosuccinate was prepared. The above two mixed solutions were combined and emulsified and dispersed at high speed using a homogenizer, and then ethyl acetate was removed to obtain a fine particle dispersion having a solid content of 15.0%. The particle diameter of the fine particles in the fine particle dispersion was 80 nm in terms of volume average particle diameter as measured with a particle size distribution measuring device “LB-500” manufactured by Horiba, Ltd. Hereinafter, this is abbreviated as a fine particle dispersion (D1).

(Production of water-soluble vinyl copolymer)
A water-soluble vinyl copolymer resin having the following vinyl monomer composition was prepared according to the procedure described below.
· Styrene ··· 15 parts · Methacrylic acid ··· 40 parts · 2-hydroxyethyl acrylate ··· 45 parts Here, the mass ratio between the vinyl monomers is the same as that of the monomer (A). The mass ratio of the body (B) is 1: 2.66, and the mass ratio of the monomer (A) and the monomer (C) is 1: 3.

  According to the above composition, each vinyl monomer was dissolved in dimethylformamide, and 3 g of α, α'-azobisisobutyronitrile was added to prepare a reaction solution. The reaction was heated at reflux at 60 ° C. for 1 hour. Thereafter, hexane was added to the reaction solution to obtain a white precipitate. The precipitate was vacuum dried to remove the solvent to obtain a powdery resin. When the infrared spectrum of this powdery resin was measured, it was confirmed to be a styrene, methacrylic acid and 2-hydroxyethyl acrylate copolymer. Moreover, when the molecular weight of this resin was measured by gel filtration chromatography (GPC), the weight average molecular weight of this resin was 3500 in polystyrene conversion. Hereinafter, this is abbreviated as a water-soluble vinyl copolymer (V1).

(Preparation of ink composition)
In accordance with the following formulation, the fine particle dispersion (D1) and the water-soluble vinyl copolymer (V1) are charged into a part of the solvent and mixed, and the mixture is stirred using a three roll and a bead mill and colored resin dispersion Got. Separately, other blending components were added to the remainder of the solvent, and stirred to dissolve and disperse to obtain a binder solution. Next, the above colored resin dispersion was added to the binder solution little by little and sufficiently stirred with a dissolver to prepare the desired aqueous inkjet printing ink (01).

<Ink composition>
-Fine particle dispersion (D1) ... 50 parts-Water-soluble vinyl copolymer (V1) ... 5 parts-Diethylene glycol ... 5 parts-Glycerin ... 15 parts-Diethanolamine ... ... 1 part ・ Polyethylene glycol (average ethylene oxide repeat number 10) end-terminal 2-butyloctanoic acid ester ………… 1 part ・ water ……… 100 parts in total

[Example 2]
In Example 1, except that the oil-soluble compound (a) used in (Preparation of fine particle dispersion) was changed to the following oil-soluble compound (b), the fine particle dispersion (D2) was obtained in the same manner as in Example 1. Prepared. Next, an aqueous inkjet printing ink (02) was prepared in the same manner. The volume average particle size of the fine particle dispersion (D2) was 85 nm.

[Example 3]
In Example 1, except that the oil-soluble compound (a) used in (Preparation of fine particle dispersion) was changed to the following oil-soluble compound (c), the fine particle dispersion (D3) was prepared in the same manner as in Example 1. Prepared. Next, an aqueous inkjet printing ink (03) was prepared in the same manner. The volume average particle diameter of the fine particle dispersion (D3) was 75 nm.

[Comparative Example 1]
In Example 1, except that the oil-soluble compound (a) used in (Preparation of fine particle dispersion) was changed to the following oil-soluble compound (d) and the hydrophobic polymer (P-2) was not used. In the same manner as in Example 1, a fine particle dispersion (D4) was prepared. Next, an aqueous inkjet printing ink (04) was prepared in the same manner. The volume average particle diameter of the fine particle dispersion (D4) was 85 nm.

[Comparative Example 2]
In Example 1, except that the oil-soluble compound (a) used in (Preparation of fine particle dispersion) was changed to the following oil-soluble compound (e) and the hydrophobic polymer (P-2) was not used. A fine particle dispersion (D5) was prepared in the same manner as in Example 1. Next, an aqueous inkjet printing ink (05) was prepared in the same manner. The volume average particle diameter of the fine particle dispersion (D5) was 87 nm.

[Comparative Example 3]
In Example 1, except that the oil-soluble compound (a) used in (Preparation of fine particle dispersion) was changed to the following oil-soluble compound (f) and the hydrophobic polymer (P-2) was not used. In the same manner as in Example 1, a fine particle dispersion (D6) was prepared. Next, an aqueous inkjet printing ink (06) was prepared in the same manner. The volume average particle diameter of the fine particle dispersion (D6) was 92 nm.

(Ink performance evaluation)
About each ink-jet printing ink (01-06) obtained above, Tokyo Keiki Co., Ltd. B-type viscometer and Kyowa Interface Science Co., Ltd. plate type surface tension meter "CBVP-A3" are used. The viscosity and surface tension were measured, and the results are shown in Table 1 below.
The inks for ink jet printing (01 to 03) obtained in Examples 1 to 3 were ejected on a glass substrate for 10 minutes using an ink jet printer, but each ink had no nozzle clogging at the nozzle tip or the like, and was ejected. The dots after landing were very good and stable. On the other hand, the ink-jet inks (04 to 06) obtained in Comparative Examples 1 to 3 had no problem in ejection properties, but were unstable due to dot spreading and blurring after landing.

(Production of color filter)
A black resist ("trade name CK-S171X" manufactured by Fuji Film Orin Co., Ltd.) is applied on a glass substrate ("1737" manufactured by Corning) by a spin coat method, and black as shown in FIG. A matrix (2) was formed. The black matrix has an opening of 70 μm × 220 μm and a film thickness of 2 μm.

Using an inkjet printing device in the opening of the black matrix, as shown in the colored pixel pattern of FIG. 3, each of the colors using the inkjet printing ink (Examples 01 to 03, Comparative Examples 04 to 06) is used. A pattern was prepared. Since the inks of the present embodiment and the comparative example are yellow (Y), magenta (M), and cyan (C) colors, the creation of blue (B), green (G), and red (R) colors is Y, M , C was performed with secondary colors composed of two types of inks (ie, B color was M and C, G color was Y and C, and R color was M and Y).
The pixels adjacent in the short side direction of the opening of the black matrix (2) are arranged in the order of R, G, and B, and the colored pixels adjacent in the long side direction of the opening are arranged in the same color. Each ink was applied in the same manner. After discharging the ink, a heat treatment was performed at a temperature of 100 ° C. for 10 minutes and at a temperature of 200 ° C. for 1 hour to cure the solid content in the ink, thereby forming a colored pixel (3) as shown in FIG.

  Subsequently, a protective film was formed on the colored pixels. The protective film was formed by applying a two-component thermosetting resin (“SS-6500” manufactured by JSR) by a spin coating method and then performing a heat treatment at a temperature of 230 ° C. for 1 hour to cure. . The film thickness after this heat treatment was about 1 μm. Furthermore, a transparent electrode was formed on the protective film. For the transparent electrode, a mixture of indium oxide and tin oxide was formed on the protective film by sputtering. The film thickness of this transparent electrode layer was about 100 nm.

The color filter substrate thus produced was tested for ejection stability, transparency, heat resistance, and fading, evaluated according to the following criteria, and the results are shown in Table 2 below.
[Evaluation criteria]
○ ……… Excellent.
Δ: Some problems were recognized.
× ……… There is a problem and cannot be put to practical use.

  The ink composition comprising the resin composition of the present invention is excellent in ejection stability, and the color filter substrate produced using this ink by the ink jet printing method is excellent in transparency, heat resistance and fading.

It is a cross-sectional schematic diagram which shows one Embodiment of the color filter substrate of this invention. It is a cross-sectional schematic diagram which shows the process of one Embodiment of the manufacturing method of the color filter substrate of this invention. It is a schematic diagram which shows one Embodiment of the colored pixel pattern of the color filter substrate of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ......... Transparent board | substrate 2 ......... Black matrix 3 ......... Colored pixel 4 ......... Protective film 5 ......... Transparent electrode layer 6 ......... Recess for pixel 7 ......... Ink 8 ......... Inkjet Printing device 9 ... Inkjet nozzle

Claims (12)

  A resin composition comprising at least (1) a fine particle dispersion containing an oil-soluble compound and a hydrophobic polymer, (2) a water-soluble resin having thermal crosslinkability, and (3) water.   The resin composition according to claim 1, wherein the water-soluble resin having thermal crosslinkability contains a water-soluble resin having an unsaturated double bond in a main chain or a side chain.   The resin composition according to claim 1 or 2, wherein the water-soluble resin having thermal crosslinkability contains a water-soluble resin having two types of functional groups capable of condensation polymerization in a side chain.   The resin according to any one of claims 1 to 3, wherein the water-soluble resin having thermal crosslinkability contains a water-soluble resin having a nucleophilic functional group and an electrophilic functional group in a side chain. Composition.   5. The resin composition according to claim 1, wherein the fine particle dispersion has an average particle diameter of 0.01 to 0.5 μm and a specific gravity of 0.9 to 1.2. Stuff.   The resin composition according to claim 1, wherein the resin composition has a viscosity of 30 mPa · s or less.   The resin composition according to claim 1, wherein a surface tension of the resin composition is 20 to 55 mN / m.   The resin composition according to claim 1, wherein the oil-soluble compound is an oil-soluble dye. 9. The resin composition according to claim 8, wherein the oil-soluble compound is an azo dye having at least one heterocyclic ring, or a phthalocyanine dye having at least a —SO— or —SO ₂ — bond.   A resin composition for a color filter substrate, which is produced by an ink jet printing method using the resin composition according to claim 1.   (1) including a step of providing a pixel layer by an inkjet printing method using the resin composition for a color filter substrate according to claim 10 on a transparent substrate, and (2) a step of curing the pixel layer by a heat treatment. A method for producing a color filter substrate characterized by   A color filter substrate manufactured by the method according to claim 11.

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