JP2010174143A - Pigment material and pigment material dispersion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment material including fine and homogeneous pigment particles, and a pigment material dispersion excellent in dispersibility obtained by using the same. <P>SOLUTION: A fine pigment material includes a fine particle of an organic pigment obtained by bringing an organic pigment solution in a good solvent into contact with a poor solvent to be deposited, and a compound of the following general formula (I): P-(X-R)n, wherein P represents an optionally substituted organic pigment structural residue or a heterocyclic residue, X represents any one of 3-30C aliphatic hydrocarbon, aryl, aralkyl, oxyalkylene, and n represents an integer of 1-4. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a dye substance and a dye substance dispersion containing fine dispersible pigment particles.

Various improved technologies have been proposed as a method for producing a fine pigment dispersion using a liquid phase method.
For example, a method for producing organic pigment particles in which secondary aggregation of particles is suppressed by using a nitrogen-containing polymer compound in combination with a compound having an amino group having a specific structure or a polymer compound having an acidic group has been proposed. (See Patent Document 1). In the method of this document, the aggregation of the pigment in the solvent when the pigment is precipitated is suppressed, but the dispersibility when the pigment is dispersed in a solvent different from the solvent at the time of precipitation is not described in this document. . Further, as a result of investigations by the present inventors, when pigment fine particles are taken out from the pigment dispersion obtained by the method described in the document and dispersed in another solvent, it is very difficult to take out the pigment. I understood that. That is, even if it is attempted to separate the pigment and the solvent from the obtained pigment solution by means such as filtration or centrifugation, there is a problem that the separation efficiency is very low due to the good dispersibility of the pigment particles, and the productivity is extremely low. there were. If the purpose is only to take out the pigment particles, the solvent can be removed by evaporating it under reduced pressure, heating, or the like, but this is not desirable because it requires extra energy. Furthermore, there is a problem that it is difficult to remove unnecessary components such as inorganic ions obtained by the alkali used at the time of dissolving the pigment and the acid used for the neutralization by the solvent evaporation method.

Also, by mixing a pigment solution obtained by dissolving a polymer compound and a pigment that are poorly soluble in a poor solvent in an aprotic solvent in the presence of an alkali with the poor solvent of the pigment, a high dispersibility is achieved. A method of obtaining a liquid composition containing molecular pigment fine particles has been proposed (see Patent Document 2). According to this method, as described in the examples of this document, when the main component of the solvent of the target pigment dispersion is the same as the poor solvent at the time of pigment precipitation, the pigment dispersion is surely excellent in dispersion stability. However, when the pigment fine particles obtained once with a poor solvent are dispersed in a solvent having a composition different from that of the poor solvent, it is difficult to maintain dispersion stability.
For example, after obtaining a pigment dispersion using water as a poor solvent, the pigment powder is taken out once through concentration and drying by filtration, and the pigment powder is dispersed in an organic solvent different from water. Aggregation of fine particles and increase in viscosity of the dispersion occur. Dispersibility in an organic solvent requires the use of a pigment derivative (described as a crystal growth inhibitor in Patent Document 2) well known in the art, and further improvement has been desired.

  Furthermore, after the pigment fine particle dispersion formed by the liquid phase method is concentrated into a paste, the resulting paste is dispersed using a polymer dispersant having a specific structure to finely disperse the nano-sized fine particles. A method for obtaining a dispersed liquid has been proposed (see Patent Document 3). However, this method has a problem that the productivity of the solvent extraction, centrifugation step and filtration step used as a method for obtaining a paste is low. In particular, when a water-soluble polymer such as polyvinylpyrrolidone is used, the low productivity in solvent extraction and centrifugation has not been practical.

  On the other hand, pigment derivatives having an alkyl group structure as a substituent of the pigment derivative are proposed in the following Patent Documents 4, 5 and the like. These technologies disclose effects in special applications such as improvement in warpage when pigments are dispersed in plastics and reduction in viscosity in inks containing special resins. There is no description or suggestion regarding the filterability of the fine particle pigment dispersion obtained by the phase method and the dispersibility of the dispersion. In addition, conventional attempts to improve pigment dispersibility with pigment derivatives have been generally carried out with compounds having a polar group such as an acidic group or a basic group in the pigment skeleton (see Patent Documents 6, 7, and 8). ).

JP 2007-23169 A JP 2007-119586 A JP 2007-262378 A Special table 2007-514798 gazette JP-A-6-49386 JP-A-5-194873 JP-A-4-246470 JP-A-8-188733

  An object of the present invention is to provide a coloring matter material containing fine and uniform pigment particles, and a coloring matter dispersion excellent in dispersibility using the coloring matter material.

The above problems have been achieved by the following means.
(1) Fine pigment substance comprising organic pigment fine particles obtained by precipitation by contact between an organic pigment solution dissolved in a good solvent and a poor solvent, and a compound represented by the following general formula (I) .
Formula (I)
P- (XR) n
(Wherein P is an organic dye structure residue or heterocyclic residue which may have a substituent, X is a direct bond or a divalent linking group, R is an aliphatic hydrocarbon group having 3 to 30 carbon atoms, An aryl group, an aralkyl group, or an oxyalkylene group is represented, and n represents an integer of 1 to 4.)
(2) The coloring matter substance according to (1), wherein the organic pigment fine particles are precipitated in the presence of the compound represented by the general formula (I).
(3) The mixing of the organic pigment fine particles and the compound represented by the general formula (I) is performed after the precipitation of the organic pigment fine particles, (1) Pigment material.
(4) The coloring matter according to any one of (1) to (3), wherein at least a part of the good solvent is removed after the organic pigment fine particles are deposited.
(5) The compound represented by the general formula (I) is represented by the following general formula (I)-(1), according to any one of (1) to (4), Pigment material.

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 3 to 30 carbon atoms, an aryl group, an aralkyl group, or an oxyalkylene group. R ² , R ³ , R ^4, and R ⁵ are each independently selected. Represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.)
(6) A pigment substance dispersion comprising the pigment substance according to any one of (1) to (5) and a dispersion solvent having a composition different from that of the good solvent.
(7) The dispersion solvent is substantially composed of at least one selected from the group consisting of ether solvents, ester solvents, ketone solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents. (4) The coloring matter dispersion according to (6).

  The coloring matter of the present invention contains fine and uniform pigment fine particles and can be dispersed in a dispersant with good dispersibility. When this pigment substance dispersion is used, a high contrast can be obtained when used for a color filter or the like.

The compound represented by formula (I) of the present invention will be described.
Formula (I)
P- (XR) n
In the formula, P is an organic dye structure residue or heterocyclic residue (n-valent organic group containing a heterocyclic ring) which may have a substituent, X is a direct bond or a divalent linking group, and R is carbon. It represents any of an aliphatic hydrocarbon group having 3 to 30 atoms, an aryl group, an aralkyl group, and an oxyalkylene group, and n represents an integer of 1 to 4.

  The organic dye structure or heterocyclic ring is not particularly limited. More specifically, examples of the organic dye structure include phthalocyanine compounds, insoluble azo compounds, azo lake compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, diketopyrrolo Examples include pyrrole compounds, anthrapyridine compounds, ansanthrone compounds, indanthrone compounds, flavanthrone compounds, perinone compounds, perylene compounds, and thioindigo compounds. Examples of the heterocyclic ring include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, Morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone, benzimidazole, adenine, etc. Is mentioned.

Further, the organic dye structure or heterocyclic ring may have a substituent group T ^1, examples of the substituent T ^1, for example, an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a phenyl group An aryl group having 6 to 16 carbon atoms such as a naphthyl group, an acyloxy group having 1 to 6 carbon atoms such as an acetoxy group, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, and a halogen such as chlorine and bromine C2-C7 alkoxycarbonyl group such as atom, methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, carbonic acid ester group such as cyano group, t-butyl carbonate, hydroxyl group, amino group, carboxyl group, sulfonamide group And N-sulfonylamide group.

  X represents a single bond or a divalent linking group. The linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. It may be unsubstituted or may further have a substituent. X is preferably an organic linking group.

Specific examples of X include the following structural units or groups formed by combining the structural units. In addition, the linking group X may have the substituent T ¹ .

The “divalent linking group” represented by X is a linear, branched, or cyclic alkylene group, arylene group, aralkylene group, —O—, —, which may have a substituent. S—, —C (═O) —, —NH (R ¹⁹ ) —, —SO—, —SO ₂ —, —CO ₂ —, or —N (R ²⁰ ) SO ₂ —, or these groups are represented by 2 One or more combined divalent groups are particularly preferred (the R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.). Of these, an organic linking group is preferred.

In general formula (I), R represents a C3-C30 aliphatic hydrocarbon group, an aryl group, an aralkyl group, and an oxyalkylene group.
The aliphatic hydrocarbon group is a linear, branched or cyclic alkyl chain (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 4 to 18 carbon atoms. For example, iso -Propyl, n-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-stearyl, n-hexadecyl, 2-ethylhexyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, most preferably 3 to 12 carbon atoms, such as allyl, 2-butenyl, 3-pentenyl, etc. ), An alkynyl group (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 3 to 12 carbon atoms). Ri, for example propargyl and 3-pentynyl.). Among these, an alkyl group is preferable.
The aryl group is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (for example, phenyl, naphthyl etc.), more preferably a phenyl group having 6 to 20 carbon atoms or 10 to 10 carbon atoms. 24 naphthyl group, more preferably a phenyl group having 6 to 12 carbon atoms or a naphthyl group having 10 to 16 carbon atoms.
The aralkyl group means a lower alkyl group substituted with an aryl group, and the alkyl part is linear or branched, preferably has 1 to 5 carbon atoms, more preferably 1, and the aryl part is preferably carbon. The number is 6 to 10, more preferably 6 to 8. Specific examples include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
An oxyalkylene group refers to a structure in which an oxygen atom is introduced into an alkylene chain. The alkylene chain may be linear, branched or cyclic. Moreover, 1-30 are preferable, as for carbon number, 2-20 are more preferable, and 4-18 are the most preferable. Moreover, 1-15 are preferable, as for the number of oxygen introduce | transduced, 2-10 are preferable, and 2-6 are the most preferable.

  The aliphatic hydrocarbon group, aryl group and aralkyl group represented by R may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom). -12, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, Rugyl, 3-pentynyl, etc.), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl) ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like. ), An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy). An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, , Formyl, pivaloyl, etc.), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc. An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl). An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), a carbamoyl group (preferably having a carbon number) 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, Examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably carbon). 6 to 20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably carbon atoms). 1 to 16, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), sulfinyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon atoms). 1 to 12, for example, methanesulfinyl, benzenesulfinyl, etc.), halogen atom (for example, fluorine atom, chlorine atom) Bromine atom, iodine atom), a cyano group and a nitro group. These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.

  In the compound represented by the general formula (I) of the present invention, the compound represented by the following general formula I- (1) is particularly preferable.

In the formula, R ¹ represents the same meaning as R.
In the formula, R ² , R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom or a cyano group.
R ² , R ³ , R ⁴ and R ⁵ in general formula (I) are preferably hydrogen atoms, that is, general formula I- (1) is represented by general formula I- (2). A structure is preferred.

R ¹ in general formulas I- (1) and I- (2) is more preferably a linear, branched or cyclic alkyl group. The number of carbon atoms in R ¹ is preferably from 1 to 30, more preferably from 1 to 20 carbon atoms, 4 to 18 carbon atoms are most preferred. For example, methyl, ethyl, iso-propyl, n-butyl, tert-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-stearyl, n-hexadecyl, 2-ethylhexyl, cyclopropyl, cyclopentyl And n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl and n-stearyl are more preferable.
Hereinafter, preferred specific examples represented by the general formulas I- (1) and I- (2) will be given, but the present invention is not limited thereto.

  Many of the compounds represented by the above general formula I- (1) are white solids and do not impair the original color characteristics of the pigments. Therefore, they can be used for almost all commercially available pigments and are preferable. .

In the case of exhibiting a hue similar to that of the pigment used in combination, a compound colored as the compound represented by the general formula (I) can also be preferably used. Specifically, those in which P in the general formula (I) is a colored organic dye structure or heterocyclic ring-containing structure can be preferably used.
When P has an organic dye structure, it is preferably an organic dye structure having the same skeleton as the pigment molecule used in combination. As the organic dye structure or heterocyclic structure particularly preferable as P, benzimidazole, quinacridone, anthraquinone, diketopyrrolopyrrole and phthalocyanine are particularly preferable.
Examples of preferred compounds are listed below.

In the present invention, the compound represented by formula (I) is preferably used as a dispersion aid for the fine pigment substance, and the amount used is not particularly limited, but if it is too small, it is difficult to obtain the effect as a dispersion aid. If it is too much, it may cause adsorption inhibition of the dispersant to be used together, so it is preferably used in a mass ratio of 0.5% to 100%, preferably 3% to 20% with respect to the pigment. Is more preferable.
Moreover, although the compound of general formula (I) may use one type of compound independently, it can also carry out preferably to use a several compound together. When a plurality of compounds are used in combination, it is preferably used so that the total amount of the compound of the general formula (I) falls within the above range.
When a plurality of compounds are used in combination, the structures of P in the general formula (I) may be the same or different from each other. However, by using compounds having different structures in combination, they may act on different surfaces of the pigment crystal. Since it may be possible, it is more preferable to use compounds having different structures in combination with P.

  In the present invention, the addition timing and introduction method of the compound represented by the general formula (I) are not particularly limited, and can be used at any timing up to the preparation of the pigment substance. Specifically, (i) a method of dissolving in a good solvent together with the pigment, (ii) preparing a dispersion aid solution in which the compound represented by the general formula (I) is dissolved separately from the pigment, the pigment solution and the poor solvent A method of adding and mixing simultaneously at the time of mixing, (iii) a method of adding and mixing a dispersion aid solution separately prepared to a mixed solution of a good solvent and a poor solvent after the precipitation of the pigment in the poor solvent is completed, and (iv) a precipitated pigment A method of adding a dispersion aid solution to the pigment composition after removing unnecessary ions and solvent from the good solvent poor solvent mixed solution containing particles by filtration and washing with water, and (v) adding insoluble ions and solvent to the pigment composition. A method of mixing the concentrated pigment material into a paste and then mixing this paste with the dispersion aid solution. (Vi) A paste material obtained by concentration or a powder pigment material obtained by drying is again used as a solvent. When dispersing, paste or powder And a method of both mixed with the coloring matter substance dispersed, any method is preferably applicable.

  Among these methods, the method of dissolving the compound represented by formula (I) together with a pigment together with a good solvent is a mixed fine particle containing both a dispersion aid and a pigment by precipitating together with the pigment upon contact with a poor solvent. The compound represented by the general formula (I) is preferably functioned as a dispersion aid to facilitate the effective action on the pigment particles, and the good solvent poor solvent mixture containing the resulting precipitated pigment particles The effect of improving the separation between pigment particles and the solvent when removing unnecessary ions and solvents from the solution by filtration and washing with water (sedimentation and drainage during filtration when filtration is used as a separation means) Is particularly preferable from the viewpoint that can be obtained. In the case of not considering the viewpoint of separation between the pigment particles and the solvent, such as sedimentation during filtration, from the viewpoint of easily obtaining an effect as a dispersibility improver for the compound represented by the general formula (I), A compound of the general formula (I) in the form of solid, solution or dispersion is mixed with a paste-like or powder-like pigment substance obtained by washing and concentrating after particle formation. A method of dispersing in a solvent is also preferred. The method of introducing the compound of general formula (I) may be a combination of a plurality of methods as described above. When a plurality of types of compounds of general formula (I) are used in combination, the method of introducing each compound is the same. Or different.

Examples of the organic pigment used in the present invention include perylene pigments, perinone pigments, quinacridone pigments, quinacridone quinone pigments, anthraquinone pigments, anthanthrone pigments, benzimidazolone pigments, disazo condensation pigments, and disazo pigments. Pigment, azo pigment, indanthrone pigment, phthalocyanine pigment, triarylcarbonium pigment, dioxazine pigment, aminoanthraquinone pigment, diketopyrrolopyrrole pigment, thioindigo pigment, isoindoline pigment, isoindolinone Pigments, isoindoline pigments, pyranthrone pigments, isoviolanthrone pigments, and mixtures thereof.
Among them, quinacridone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine pigments, isoindoline pigments or azo pigments are preferable, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindoline pigments. A pigment or a dioxazine pigment is more preferable.

  The first solvent (good solvent) is not particularly limited as long as it can dissolve the organic pigment and is compatible with (mixed uniformly with) the second solvent (poor solvent). The solubility of the organic pigment in the first solvent is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. Although there is no particular upper limit to the solubility, it is practical that the solubility is 50% by mass or less in consideration of a commonly used organic pigment.

  As for the compatibility of the first solvent and the second solvent, the amount of the first solvent dissolved in the second solvent is preferably 30% by mass or more, and more preferably 50% by mass or more. There is no particular upper limit on the amount of the first solvent dissolved in the second solvent, but it is practical to mix them in an arbitrary ratio.

  Although it does not specifically limit as a 1st solvent, An organic acid (For example, formic acid, dichloroacetic acid, methanesulfonic acid etc.), an organic base (For example, diazabicycloundecene (DBU), tetrabutylammonium hydroxide, sodium methoxide) Etc.), aqueous solvents (for example, water, hydrochloric acid, sodium hydroxide aqueous solution), alcohol solvents (for example, methanol, ethanol, n-propanol, etc.), ketone solvents (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) , Ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.) Ester solvents (for example, ethyl acetate, n-butyl acetate, ethyl lactate, etc.), amide solvents (for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), ionic liquids (for example, And 1-ethyl-3-methylimidazolium tetrafluoroborate), a carbon disulfide solvent, or a mixture thereof.

  Among these, an organic acid, an organic base, an aqueous solvent, an alcohol solvent, a ketone solvent, an ether solvent, a sulfoxide solvent, an ester solvent, an amide solvent, or a mixture thereof is more preferable, and an organic acid, an organic base , Sulfoxide solvents, amide solvents, or mixtures thereof are particularly preferred.

  Examples of the organic acid include, but are not limited to, sulfonic acid compounds, carboxylic acid compounds, acid anhydride compounds, and the like.

Examples of the sulfonic acid compound, alkyl sulfonate, halogenated alkylsulfonic acids, and aromatic sulfonic acids and the like, alkyl chains or aromatic rings may be unsubstituted or may be substituted with a substituent T ² . The substituent T ² here may be any substituent as long as it can be substituted with the sulfonic acid compound.

Examples of the substituent T ² include an aliphatic group, an aryl group, a heterocyclic group, an acyl group, a nitro group, an amino group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a heterocyclic oxy group, and an aliphatic group. Group oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, heterocyclic sulfonyloxy group, Sulfamoyl group, aliphatic sulfonamido group, aryl sulfonamido group, heterocyclic sulfonamido group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, Heterocyclic oxycarbonyl Amino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxyl group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoyl Examples thereof include an amino group, a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl group, and a diaryloxyphosphinyl group.

  Specific examples of the sulfonic acid compound used in the present invention include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nona. Fluorobutanesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, xylenesulfonic acid, dodecylbenzenesulfonic acid, naphthalenesulfonic acid, chlorobenzenesulfonic acid, aminobenzenesulfonic acid, 1,5-naphthalenedisulfonic acid tetrahydrate, etc. It is done.

Examples of the carboxylic acid compound include alkyl carboxylic acids, halogenated alkyl carboxylic acids, and aromatic carboxylic acids. The alkyl chain and the aromatic ring may be unsubstituted or substituted with the substituent T ^2. . Specific examples of carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, difluoroacetic acid, dichloroacetic acid, dibromoacetic acid, fluoroacetic acid, chloroacetic acid, bromoacetic acid, chlorodifluoroacetic acid , Cyanoacetic acid, phenoxyacetic acid, diphenylacetic acid, thioacetic acid, mercaptoacetic acid, mercaptopropionic acid, 2-chloropropionic acid, 2,2-dichloropropionic acid, 3-chloropropionic acid, 2-bromopropionic acid, 3-bromopropion Acid, 2,3-dibromopropionic acid, 2-chlorobutyric acid, 3-chlorobutyric acid, 4-chlorobutyric acid, isobutyric acid, 2-bromoisobutyric acid, cyclohexanecarboxylic acid, nitroacetic acid, phosphonoacetic acid, pyruvic acid, oxalic acid, propargyl Acid, trimethylammonium acetic acid Benzoic acid, tetrafluorobenzoic acid, pentafluorobenzoic acid, 2-chlorobenzoic acid, 2-fluorobenzoic acid, benzoyl formate, benzoylbenzoic acid, 2-dimethylaminobenzoic acid, 2,6-dihydroxybenzoic acid, picolinic acid, Citric acid, cysteine, sulfanilic acid, squaric acid and the like can be mentioned.

  In the present invention, in addition to carboxylic acid and sulfonic acid, an acid anhydride can be used as the acid, and specifically, acetic anhydride, propionic acid anhydride, trifluoromethanesulfonic acid anhydride, trichloro And acid anhydrides such as acetic anhydride. Examples of organic acids other than these include isopropyl phosphate, methyl phosphate, phenylphosphonic acid, ethylenediaminetetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and methylenediphosphonic acid.

  As the organic acid, alkylsulfonic acid, alkylcarboxylic acid, halogenated alkylcarboxylic acid, and aromatic sulfonic acid are preferable, and methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, chloroacetic acid. Formic acid, toluenesulfonic acid, and dodecylbenzenesulfonic acid are more preferable.

  Examples of organic bases include primary amines, secondary amines, tertiary amines, quaternary amines, anilines, piperidines, piperazines, amidines, formamidines, pyridines, Examples include, but are not limited to, guanidines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like. Among these, tertiary amines, quaternary amines, morpholines, nitrogen-containing heterocycles, metal alkoxides and the like are preferable.

  Specifically, aniline, 2-chloroaniline, 3-fluoroaniline, 2,4-difluoroaniline, 2-nitroaniline, N, N-diethylaniline, 2,6-diethylaniline, 2,4-dimethoxyaniline, p-phenylenediamine, pyridine, 2-aminopyridine, pyrimidine, pyridazine, pyrazine, 2,2-dipyridyl, pyrrolidine, piperidine, imidazole, pyrazole, thiazole, benzothiazole, oxazole, diazabicycloundecene, diazabicyclononene, Diazabicyclooctane, 1-cyanoguanidine, N, N′-diphenylguanidine, cyclohexylamine, butylamine, cyclopropylamine, t-butylamine, benzylamine, diisopropylamine, trimethylamine, triethylamine , Tributylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, morpholine, thiomorpholine, N-methylmorpholine, hexamethylphosphoramide, 1-methyl -4-piperidone, N- (2-aminoethyl) piperazine, ethylenediamine, diethylenetriamine, bis- (3-aminopropyl) ether, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium Examples include ethoxide and potassium t-butoxide.

  Among these, aniline, 2,4-difluoroaniline, pyridine, diazabicycloundecene, diazabicyclononene, diazabicyclooctane, triethylamine, tetrahydroquinoline, phenyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, tetramethyl Ammonium hydroxide, tetrabutylammonium hydroxide, N-methylmorpholine, N- (2-aminoethyl) piperazine, sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium -T-butoxide is preferred, 2,4-difluoroaniline, diazabicycloundecene, diazabicyclononene, tetrahydroquinoline, phenyltrimethylammonium Hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, N- methylmorpholine, sodium methoxide, potassium -t- butoxide preferred.

  More specific examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like.

  More specifically, examples of the amide solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε -Caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide and the like.

  There are no particular limitations on the conditions for preparing the organic pigment solution, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −10 to 150 ° C., more preferably −5 to 130 ° C., and particularly preferably 0 to 100 ° C.

  When the organic pigment is uniformly dissolved in the first solvent, generally, in the case of a pigment having an alkaline and dissociable group in the molecule, there is no alkali, but there is no alkaline and dissociable group, and nitrogen is easily added with protons. When there are many atoms in the molecule, it is preferable to use acidity. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation compound pigments are alkaline, and phthalocyanine compound pigments are acidic.

  In addition to the organic base, inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide can also be used as the base used when dissolving in an alkaline manner. The amount of the base to be used is not particularly limited, but in the case of an inorganic base, it is preferably 1.0 to 30 molar equivalents, more preferably 1.0 to 25 molar equivalents relative to the organic pigment. It is particularly preferably 0 to 20 molar equivalents. In the case of an organic base, it is preferably 1.0 to 100 molar equivalents, more preferably 5.0 to 100 molar equivalents, and particularly preferably 20 to 100 molar equivalents with respect to the organic pigment.

  In addition to the organic acid, an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or the like can be used as an acid used when the acid is dissolved. The amount of the acid to be used is not particularly limited, but it is often used in excess compared to the base, and is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents with respect to the organic pigment. 30 to 200 molar equivalents are particularly preferred.

  When an inorganic base or an inorganic acid is mixed with an organic solvent and used as a good solvent (first solvent) for an organic pigment, the alkali or acid is completely dissolved. On the other hand, a solvent having high solubility can be added to the organic solvent. The amount of water or lower alcohol is preferably 50% by mass or less, more preferably 30% by mass or less, based on the total amount of the organic pigment solution. Specifically, water, methanol, ethanol, n-propanol, isopropanol, butyl alcohol, or the like can be used.

  The viscosity of the organic pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

The organic pigment solution is not particularly limited as long as the organic pigment is dissolved in the first solvent, and may contain other components.
Although it does not specifically limit as another component, The organic compound which has an acidic group, the organic compound which has basicity etc. are mentioned suitably. These components have the action of adsorbing quickly to the deposited pigment and treating the pigment surface to be acidic or basic when the pigment is precipitated by mixing the organic pigment solution and the second solvent. Is. The solubility of the other components in the second solvent is not particularly limited, but is preferably a compound that makes the second solvent a poor solvent.

  Examples of the acidic group of the organic compound having an acidic group that can be used in the present invention include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a sulfenic acid group, a phosphonic acid group, a hydroxyl group, and a sulfide group. Is not to be done. Moreover, 1 type may be individual in a molecule | numerator, or 2 or more types may contain the same or different functional group. These organic compounds having an acidic group may be used alone or in combination of two or more. Among these, those having a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are preferable.

  Examples of the organic compound having a carboxylic acid group include behenic acid, 13-docosenoic acid, oleic acid, linoleic acid, stearic acid, isostearic acid, 2-hexyldecanoic acid, palmitic acid, myristic acid, lauric acid, decanoic acid, and octane. Acid, 3,5,5-trimethylhexanoic acid, 1,12-todecanedicarboxylic acid, sebacic acid, 1-adamantanecarboxylic acid, 1-naphthoic acid, 2-naphthoic acid, pyromellitic acid, p-benzoylaminobenzoic acid , Terephthalic acid, isophthalic acid, phthalic acid, benzoic acid, trimellitic acid, 1-hydroxy-2-naphthoic acid, β-oxynaphthoic acid, p-octyloxybenzoic acid, triphenylacetic acid, mandelic acid, perfluorooctanoic acid , P-nitrobenzoic acid, o-benzoylbenzoic acid, 4-sulfamoylbenzoate Acid, o-benzoylaminobenzoic acid, 2,6-pyridinedicarboxylic acid, tetrahydrofurantetracarboxylic acid, 2-quinolinecarboxylic acid, 4,4-biphenyldicarboxylic acid, 4-hydroxybiphenyl-3-carboxylic acid, 2-naphthylacetic acid 2,6-naphthalenedicarboxylic acid, 6-hydroxy-2-naphthoic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,8-naphthalic acid, 3,4,9,10-perylenetetracarboxylic acid Indole-3-butyric acid, 3,7-dicarboxylic acid diphenyl oxide, tetrachlorophthalic acid, phthalic acid, folic acid, benzylic acid, naphthenic acid, diphenylacetic acid, 2,4-dichlorobenzoic acid and the like.

  Examples of the organic compound having a sulfonic acid group include β-naphthalenesulfonic acid, dodecylbenzenesulfonic acid, cetylsulfuric acid, C acid, J acid, γ acid, diaminostilbene disulfonic acid, benzenesulfonic acid, benzenedisulfonic acid, and naphthalenesulfone. Examples thereof include acid, naphthalene disulfonic acid, chlorobenzene sulfonic acid, 1-naphthylamine-4-sulfonic acid (naphthoic acid), dobias acid, peric acid, jaic acid, kofu acid, metanilic acid, toluenesulfonic acid, octanesulfonic acid and the like.

  Examples of the compound having a sulfinic acid group include p-toluenesulfinic acid, benzenesulfinic acid, p-carboxybenzenesulfinic acid, octylsulfinic acid, ethylsulfinic acid, 4-chloro-3-nitrobenzenesulfinic acid, and 4-acetamidobenzenesulfinic acid. Thiophene-2-sulfinic acid, methylsulfinic acid, isobutylsulfinic acid, hexadecylsulfinic acid, hydroxylmethanesulfinic acid and the like.

Examples of the sulfenic acid compound include benzenesulfenic acid and p-toluenesulfenic acid.
Examples of phosphonic acid compounds include stearyl phosphonic acid and lauryl phosphonic acid.

  In the present invention, the addition amount of the organic compound having an acidic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, based on the pigment. It is especially preferable that it is in the range of 0.05 to 15% by mass.

  Organic compounds having a basic group include alkylamines, arylamines, aralkylamines, pyrazole derivatives, imidazole derivatives, triazole derivatives, tetrazole derivatives, oxazole derivatives, thiazole derivatives, pyridine derivatives, pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, triazines. Derivatives and the like can be mentioned, and alkylamine, arylamine and imidazole derivatives are preferable.

As carbon number of the organic compound which has the said basic group, 6 or more are preferable, More preferably, it is 8 or more, More preferably, it is 10 or more.
In the organic compound having a basic group, examples of the alkylamine include butylamine, amylamine, hexylamine, heptylamine, octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, isobutylamine, t-butylamine, 1-methylbutylamine, 1-ethylbutylamine, t-amylamine, 3-aminoheptane, t-octylamine, 1,4 -Diaminobutane, 1,6-hexadiamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dibutylamine, dihexylamine, dioctylamine, bis (2- Tylhexyl) amine, didecylamine, N-methyloctadecylamine, triethylamine, tripropylamine, N, N-dimethylbutylamine, N-methyldibutylamine, tributylamine, tripentylamine, N, N-dimethylhexylamine, N, N- Dimethyloctylamine, N-maledioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyl-N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N-methylcyclohexylamine, N, N, N ′, N ′, N "-Pentamethyldiethylenetria , Cyclohexylamine, cycloheptylamine, cyclohexylamine, cyclododecylamine, 1-adamandanamine, etc., preferably octylamine, 2-hexylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecyl Amine, tetradecylamine, octadecylamine, t-octylamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, N- Methyl octadecylamine, N, N-dimethyloctylamine, N-mail dioctylamine, trioctylamine, triisooctylamine, N, N-dimethyldodecylamine, tridodecylamine, N-methyl -N-octadecyl-1-octadecylamine, N, N-dibutylethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyl-1,6-hexanediamine, N -Methylcyclohexylamine, N, N, N ', N', N "-pentamethyldiethylenetriamine, cyclododecylamine, 1-adamandanamine and the like, more preferably decylamine, undecylamine, dodecylamine, tri Examples include decylamine, tetradecylamine, didecylamine, N-methyloctadecylamine, N, N-dimethyldodecylamine, and tridodecylamine. Organic polymer compounds having a basic group such as polyallylamine and polyvinylamine are also suitable.

  As the arylamine, for example, N, N-dibutylaniline, 4-butylaniline, 4-pentylamine, 4-hexylamine, 4-heptylaniline, 4-octylaniline, 4-decylaniline, 4-dodecylaniline, 4 -Tetradecylaniline, 4-hexadecylaniline, 4-butoxyaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, and the like, preferably 4-octylaniline, 4-decylaniline 4-dodecylaniline, 4-tetradecylaniline, 4-hexadecylaniline, 4-pentyloxyaniline, 4-hexyloxyaniline, 4-hexyloxyaniline, etc., more preferably 4-decylaniline, 4 -Dodecylaniline, 4 Tetradecyl aniline, 4-hexadecyl aniline, 4-pentyloxy aniline, 4-hexyloxy aniline, 4-hexyloxy aniline.

  Examples of the imidazole derivative include 1- (10-hydroxydecyl) imidazole, 1-butylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and the like.

  The organic compound having a basic group is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.05 to 20% by mass, and more preferably 0.05 to 15% with respect to the pigment. It is particularly preferable to be in the range of mass%.

It is also preferable to add an organic compound composed of a basic group and a heterocyclic group.
Examples of such an organic compound include 2-aminopyridine, 3-aminopyridine, 1- (2-aminophenyl) pyrrole, 5-aminopyrazole, 3-amino-5-methylpyrazole, 5-amino-1- Ethylpyrazole, 3-aminotriazole, 2-aminothiazole, 5-aminoindole, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, phthalimide, 5-aminobenzimidazolone N, N-dimethyl-5-aminobenzimidazolone, 5-aminouracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, aminopyrazine, 8-aminoquinoline, 3-aminoquinoline, 9-amino Acridine, ASTRA blue 6GLL (base Phthalocyanine derivative), 2-amino-anthraquinone, 3-amino-anthraquinone, acridone, N- acridone, quinacridone, NILE Red, and the like methylene violet naphthalimide is. Preferably, 2-aminobenzthiazole, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone, 5-amino Uracil, 6-aminouracil, uracil, thymine, adenine, guanine, melamine, 8-aminoquinoline, 3-aminoquinoline, 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoanthraquinone, 3-amino Anthraquinone, acridone, N-acridone, quinacridone, NILE red, methylene violet naphthalimide, and more preferably 9-aminoacridine, ASTRA blue 6GLL (basic phthalocyanine derivative), 2-aminoan Laquinone, 3-aminoanthraquinone, acridone, N-acridone, 5-aminobenzimidazole, N, N-dimethyl-5-aminobenzimidazole, 5-aminobenzimidazolone, N, N-dimethyl-5-aminobenzimidazolone , 5-aminouracil, 6-aminouracil, NILE red, and methylene violet naphthalimide.

  The addition amount of the organic compound composed of the basic group and the heterocyclic group is preferably in the range of 0.01 to 30% by mass, and in the range of 0.05 to 20% by mass with respect to the pigment. It is more preferable that it is in the range of 0.05 to 15% by mass.

  In addition to the above, pigment derivatives described in JP-A No. 2007-9096 and JP-A No. 7-331182 can be exemplified. The pigment derivative referred to here is derived from a pigment derivative compound derived from an organic pigment as a parent substance and manufactured by chemically modifying the parent structure, or by a pigmentation reaction of a chemically modified pigment precursor. Refers to a pigment derivative type compound. Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative)” manufactured by Lubrizol (all are trade names), and the like. When a pigment derivative is used, the amount used is preferably in the range of 0.5 to 30% by mass, more preferably in the range of 3 to 20% by mass, and 5 to 15% by mass with respect to the pigment. It is especially preferable that it is in the range.

  The second solvent (poor solvent) is not particularly limited, but the solubility of the organic pigment in the second solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. Although there is no particular lower limit to the solubility of the organic pigment in the second solvent, 0.0001% by mass or more is practical in consideration of a commonly used organic pigment.

Although it does not specifically limit as a 2nd solvent, An aqueous solvent (For example, water, hydrochloric acid, sodium hydroxide aqueous solution), Alcohol-type solvent (For example, methanol, ethanol, n-propanol etc.), Ketone-type solvent (For example, methyl ethyl ketone) , Methyl isobutyl ketone, cyclohexanone, etc.), ether solvents (eg, tetrahydrofuran, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), sulfoxide solvents (eg, dimethyl sulfoxide, hexamethylene sulfoxide, sulfolane, etc.), ester solvents (For example, ethyl acetate, acetic acid-n-butyl, ethyl lactate, etc.), amide solvents (for example, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), aromatic hydrocarbon solvents ( For example, toluene, xylene, etc.), aliphatic hydrocarbon solvents (for example, octane), nitrile solvents (for example, acetonitrile), halogen solvents (for example, carbon tetrachloride, dichloromethane, etc.), ionic liquids (for example, 1-ethyl-3
-Methylimidazolium tetrafluoroborate etc.), carbon disulfide solvent, or a mixture thereof is preferably mentioned.
Among these, an aqueous solvent, an alcohol solvent, a ketone solvent, a sulfoxide solvent, an ester solvent, an amide solvent, a nitrile solvent, or a mixture thereof is more preferable, and an aqueous solvent, an alcohol solvent, or a mixture thereof. Is particularly preferred.

Examples of the aqueous solvent include water, hydrochloric acid, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and the like.
Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like.

  Although there are some that are common between those listed as specific examples of the first solvent and those listed as the second solvent, the same thing as the first solvent and the second solvent is not combined, Therefore, the solubility in the first solvent should be sufficiently higher than the solubility in the second solvent. For the pigment, for example, the solubility difference is preferably 0.2% by mass or more, and 0.5% by mass or more. Is more preferable. There is no particular upper limit to the difference in solubility between the first solvent and the second solvent, but it is practical that the difference is 50% by mass or less in consideration of a commonly used organic pigment.

  The state of the second solvent is not particularly limited, and a range from normal pressure to subcritical and supercritical conditions can be selected. The temperature at normal pressure is preferably −30 to 100 ° C., more preferably −10 to 60 ° C., and particularly preferably 0 to 30 ° C. The viscosity of the organic pigment solution is preferably 0.5 to 100.0 mPa · s, and more preferably 1.0 to 50.0 mPa · s.

  When mixing the organic pigment solution and the second solvent, either of them may be added and mixed. However, the organic pigment solution is preferably jetted into the second solvent and mixed, and in this case, the second solvent is mixed. Is preferably in a stirred state. The stirring speed is preferably 100 to 10,000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm. A pump or the like may be used for the addition, or it may not be used. Moreover, although addition in a liquid or addition outside a liquid may be sufficient, addition in a liquid is more preferable. Further, it is preferable to continuously supply the liquid into the liquid through a supply pipe. The inner diameter of the supply pipe is preferably 0.1 to 200 mm, more preferably 0.2 to 100 mm. As a speed | rate supplied into a liquid from a supply pipe | tube, 1-1000 ml / min is preferable and 5-5000 ml / min is more preferable.

By adjusting the Reynolds number when mixing the organic pigment solution and the second solvent, it is possible to control the particle diameter of the pigment nanoparticles to be deposited. Here, the Reynolds number is a dimensionless number representing the state of fluid flow and is represented by the following equation.
Re = ρUL / μ Equation (1)
In Formula (1), Re represents the Reynolds number, ρ represents the density [kg / m ³ ] of the organic pigment solution, and U represents the relative speed [m / s] when the organic pigment solution meets the second solvent. L represents the equivalent diameter [m] of the flow path or supply port where the organic pigment solution and the second solvent meet, and μ represents the viscosity coefficient [Pa · s] of the organic pigment solution.

The equivalent diameter L is the diameter of an equivalent circular pipe when assuming an opening diameter of a pipe having an arbitrary cross-sectional shape or a circular pipe equivalent to a flow path. The equivalent diameter L is expressed by the following equation (2), where A is the cross-sectional area of the pipe, p is the wetted length (circumferential length) of the pipe, or p is the outer periphery of the flow path.
L = 4 A / p Equation (2)
It is preferable to form particles by injecting the organic pigment solution into the second solvent through a pipe. When a circular pipe is used for the pipe, the equivalent diameter matches the diameter of the circular pipe. For example, the equivalent diameter can be adjusted by changing the opening diameter of the liquid supply port. Although the value of the equivalent diameter L is not specifically limited, For example, it is synonymous with the preferable internal diameter of the supply port mentioned above.

  The relative speed U when the organic pigment solution and the second solvent meet is defined by the relative speed in the direction perpendicular to the surface of the portion where both meet. That is, for example, when the organic pigment solution is injected and mixed in the stationary second solvent, the injection speed from the supply port becomes equal to the relative speed U. Although the value of the relative speed U is not specifically limited, For example, it is preferable to set it as 0.5-100 m / s, and it is more preferable to set it as 1.0-50 m / s.

The density ρ of the organic pigment solution is a value determined by the type of material selected, but is practically, for example, 0.8 to 2.0 kg / m ³ . Also, the viscosity coefficient μ of the organic pigment solution is a value determined by the material used, the environmental temperature, and the like, but its preferred range is synonymous with the preferred viscosity of the organic pigment solution described above.

  The smaller the Reynolds number (Re) value, the easier it is to form a laminar flow, and the larger the value, the easier it is to form a turbulent flow. For example, it can be obtained by adjusting the Reynolds number to 60 or more to control the particle diameter of the pigment nanoparticles, preferably 100 or more, and more preferably 150 or more. Although there is no particular upper limit to the number of lay nozzles, for example, favorable pigment nanoparticles can be obtained by controlling and controlling in the range of 100,000 or less, which is preferable. Or it is good also as conditions which raised Reynolds number so that the average particle diameter of the nanoparticle obtained may be 60 nm or less. At this time, within the above range, it is possible to control and obtain pigment nanoparticles having a smaller particle size by increasing the Reynolds number.

  The mixing ratio of the organic pigment solution and the second solvent is preferably 1/50 to 2/3, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8. The particle concentration in the liquid when the organic pigment fine particles are deposited is not particularly limited, but the organic pigment fine particles are preferably in the range of 10 to 40,000 mg, more preferably in the range of 20 to 30000 mg with respect to 1000 ml of the solvent. Especially preferably, it is the range of 50-25000 mg. In addition, the preparation scale for generating the organic pigment fine particles is not particularly limited, but the mixed amount of the second solvent is preferably a preparation scale of 10 to 2000 L, and more preferably a preparation scale of 50 to 1000 L. .

  Regarding the particle diameter of organic pigment fine particles or fine pigment substances, there is a method of expressing the average size of the group by quantifying it by a measurement method. Median diameter corresponding to the median of the distribution curve, various average diameters (number average, length average, area average, mass average, volume average, etc.), etc. In the present invention, unless otherwise specified, the average particle size The diameter means a volume weighted average.

  In the present invention, the average particle size of the organic pigment fine particles (primary particles) is preferably 1 nm to 1 μm in volume weighted average, more preferably 1 to 200 nm, further preferably 2 to 100 nm, 80 nm is particularly preferable. The formed particles may be crystalline particles, amorphous particles, or a mixture thereof.

  In the present invention, the ratio (Mv / Mn) of the volume average particle diameter (Mv) and the number average particle diameter (Mn) is used as an index representing the monodispersity of the particles unless otherwise specified. In the present invention, the monodispersity of the pigment fine particles (primary particles), that is, Mv / Mn, is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, -1.5 is particularly preferred.

  Examples of the method for measuring the particle size of the organic pigment fine particles include a microscopy method, a mass method, a light scattering method, a light blocking method, an electrical resistance method, an acoustic method, and a dynamic light scattering method. Is particularly preferred. Examples of the microscope used for the microscopy include a scanning electron microscope and a transmission electron microscope. Examples of the particle measuring apparatus by the dynamic light scattering method include Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd. and Dynamic Light Scattering Photometer DLS-7000 series manufactured by Otsuka Electronics Co., Ltd.

  In preparing the dispersion liquid by precipitating the organic pigment fine particles, at least the second solvent is a good solvent (solubility in the second solvent is 4.0% by mass or more) in at least one of the organic pigment solution and the second solvent. A small compound (hereinafter sometimes referred to as a particle size adjusting agent) may be contained.

Examples of the polymer particle size adjusting agent include polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, polyvinyl alcohol-partial formalized product, polyvinyl alcohol-part. Butyralized product, vinylpyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylic acid, sodium polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, a diallylamine monomer / SO ₂ copolymers, diallylamine hydrochloride / Ma Examples thereof include oleic acid copolymer, polydiallylmethylamine hydrochloride, polydiallyldimethylammonium chloride, diallyldimethylammonium chloride / acrylamide copolymer, condensed naphthalene sulfonate, cellulose derivative, starch derivative and the like. In addition, natural polymers such as alginate, gelatin, albumin, casein, gum arabic, tonganto gum and lignin sulfonate can also be used. Of these, polyvinylpyrrolidone, polyacrylic acid, polyallylamine, polyallylamine hydrochloride, polyvinylamine hydrochloride, allylamine hydrochloride / diallylamine hydrochloride copolymer, diallylamine monomer / SO ₂ copolymer, and the like are preferable. These particle size adjusting agents can be used singly or in combination of two or more.
The mass average molecular weight is preferably 1,000 to 500,000, more preferably 10,000 to 500,000, and particularly preferably 10,000 to 100,000.

  Examples of anionic particle size adjusting agents (anionic surfactants) include N-acyl-N-alkyltaurine salts, fatty acid salts, alkylsulfuric acid ester salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, and dialkylsulfosuccinates. , Alkyl phosphate ester salt, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salt and the like. Of these, N-acyl-N-alkyltaurine salts are preferred. As the N-acyl-N-alkyl taurine salt, those described in JP-A-3-273067 are preferable. These anionic particle size regulators can be used alone or in combination of two or more.

  Cationic particle size modifiers (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines derived from aliphatic amines and fatty alcohols, and Examples include salts of cationic substances of imidazoline derived from polyamines and fatty acids. These cationic particle size regulators can be used alone or in combination of two or more.

  The amphoteric particle size regulator is a particle size in which the anionic particle size regulator has both an anion group moiety in the molecule and a cationic group moiety in the molecule of the cationic particle size modifier. It is a regulator.

  Nonionic particle size adjusting agents (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples thereof include alkylamines and glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic particle size regulators may be used alone or in combination of two or more.

  The content of the particle size adjusting agent is preferably in the range of 0.1 to 100% by mass, more preferably 0.1 to 50% with respect to the pigment in order to further improve the particle size control of the pigment fine particles. It is the range of mass%, More preferably, it is the range of 0.1-20 mass%. In addition, the particle size adjusting agents may be used alone or in combination.

The organic pigment fine particles in the fine pigment material of the present invention are build-up organic pigment fine particles obtained by precipitation by contact between an organic pigment solution dissolved in a good solvent and a poor solvent, and are obtained by pulverizing a bulk pigment or the like. Different from breakdown pigment particles.
The fine pigment substance of the present invention is not particularly limited as long as it contains the organic pigment fine particles and the compound represented by the above general formula (I), but the solvent component (good) is obtained from the mixed liquid in which the organic pigment fine particles are precipitated. It is preferable that part or all of the solvent (first solvent) and the poor solvent (second solvent) be removed. In the present invention, the presence state of the compound represented by the general formula (I) with respect to the organic pigment fine particles is not particularly limited, a state of being adsorbed on the surface of the organic pigment fine particles, a state in which part or all is taken into the organic pigment fine particles, Alternatively, a state where organic pigment fine particles and a solid solution are formed is preferable. However, in order to achieve a higher effect, it is desirable that at least a part of the compound represented by the general formula (I) is present on the surface of the organic pigment particle, and it is adsorbed on the surface of the organic pigment particle or partially A state in which the organic pigment is incorporated in the fine particles of the organic pigment is preferable.

The process for removing the solvent from the mixed liquid after the organic pigment fine particles are deposited is not particularly limited, and examples thereof include a method of filtering with a filter and the like, a method of precipitating and concentrating the organic pigment fine particles by centrifugation.
As an apparatus for filter filtration, for example, an apparatus such as reduced pressure or pressure filtration can be used. Examples of preferable filters include filter paper, nanofilters, and ultrafilters.
Any device may be used as the centrifuge as long as the organic pigment fine particles can be precipitated. For example, in addition to a general-purpose device, a device having a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system), a continuous centrifuge that continuously discharges solid matter, and the like can be mentioned. Centrifugation conditions are preferably 50 to 10,000, more preferably 100 to 8000, and particularly preferably 150 to 6000 in terms of centrifugal force (a value representing how many times the gravitational acceleration is applied). Although the temperature at the time of centrifugation is based on the solvent seed | species of a dispersion liquid, -10-80 degreeC is preferable, -5-70 degreeC is more preferable, and 0-60 degreeC is especially preferable.
In addition, as the solvent removal step, a method of concentrating the solvent by sublimation by vacuum freeze-drying, a method of drying and concentrating the solvent by heating or decompression, a method combining them, or the like can also be used.

The fine pigment substance can be made into a pigment substance dispersion (hereinafter sometimes simply referred to as a pigment dispersion) using a dispersion solvent (third solvent) having a composition different from that of the first solvent.
Although the kind of 3rd solvent is not specifically limited, It is preferable that it is an organic solvent, for example, an ether solvent, an ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, and an aliphatic hydrocarbon solvent are preferable. The third solvent may be a pure solvent based on the above solvent or a mixed solvent composed of a plurality of solvents.
In the present invention, any one of the good solvent (first solvent) and the poor solvent (second solvent) used as a dispersion medium is not limited to the third solvent but includes a fourth solvent described later. These different solvents are collectively referred to as “third solvent”.

  Examples of the ether solvent include tetrahydrofuran, propylene glycol monomethyl ether, and the like. Examples of the ester solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the ketone solvent include methyl ether ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and the like. Examples of the aliphatic hydrocarbon solvent include n-hexane and cyclohexane.

  Of these, ethyl lactate, ethyl acetate, and 2- (1-methoxy) propyl acetate are preferable, and ethyl lactate and 2- (1-methoxy) propyl acetate are more preferable. These may be used alone or in combination of two or more. The third solvent is not the same as the first solvent or the second solvent.

  The amount of the third solvent added is not particularly limited, but is preferably 100 to 300,000 parts by mass, and more preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the organic pigment fine particles.

  The organic pigment fine particles can be used, for example, in a dispersed state in a vehicle. The vehicle refers to a portion of a medium in which a pigment is dispersed when it is in a liquid state, a portion that is liquid and binds to the pigment to harden a coating film (binder). And a component (organic solvent) to be dissolved and diluted. In the present invention, the polymer compound used for forming the organic pigment fine particles and / or the pigment dispersant used for redispersion are collectively referred to as a binder.

  The concentration of organic pigment fine particles in the dispersion of organic pigment fine particles after redispersion is appropriately determined according to the purpose. Preferably, the organic pigment fine particles are preferably 2 to 30% by mass based on the total amount of the dispersion. More preferably, it is -20 mass%, and it is especially preferable that it is 5-15 mass%. When dispersed in the vehicle as described above, the amount of the binder and dissolved diluent component is appropriately determined depending on the type of organic pigment, etc., but the binder is preferably 1 to 30% by mass based on the total amount of the dispersion. 3 to 20% by mass is more preferable, and 5 to 15% by mass is particularly preferable. It is preferable that a dissolution dilution component is 5-80 mass%, and it is more preferable that it is 10-70 mass%.

  Although content of the organic pigment fine particle in the pigment | dye dispersion of this invention is not specifically limited, It is preferable that it is 1.0-35.0 mass%, and it is more preferable that it is 5.0-25.0 mass%.

  When the coloring matter of the present invention is redispersed in the third solvent, the aggregation state of the organic pigment fine particles is spontaneously solved in the third solvent and dispersed in the medium without adding another dispersant or the like. This property is referred to as “self-dispersible” or “self-dispersible”. However, in order to further improve the redispersibility in the present invention, a pigment dispersant or the like may be added during redispersion of the coloring matter.

As a method of redispersing the fine pigment substance in such an aggregated state, for example, a dispersion method using ultrasonic waves or a method of applying physical energy can be used. The ultrasonic irradiation device used preferably has a function capable of applying an ultrasonic wave of 10 kHz or higher, and examples thereof include an ultrasonic homogenizer and an ultrasonic cleaner. When the liquid temperature rises during ultrasonic irradiation, thermal aggregation of the nanoparticles occurs, so the liquid temperature is preferably 1 to 100 ° C, more preferably 5 to 60 ° C. The temperature control method can be performed by controlling the dispersion temperature, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, and the like.
There are no particular restrictions on the disperser used when dispersing the pigment substance by applying physical energy, and examples include dispersers such as kneaders, roll mills, atriders, super mills, dissolvers, homomixers, and sand mills. It is done. In addition, a high-pressure dispersion method and a dispersion method using fine particle beads are also preferable.

For the purpose of further improving the dispersibility of the pigment, conventionally known dispersants such as pigment dispersants and surfactants can be added to the dye dispersion of the present invention as long as the effects of the present invention are not impaired. .
Examples of pigment dispersants include polymer dispersants (for example, linear polymers, block polymers, graft polymers, terminal-modified polymers, etc.), surfactants (polyoxyethylene alkyl phosphate ester, poly Oxyethylene alkylamine, alkanolamine, etc.), pigment derivatives and the like. The dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. For this reason, a block polymer, a graft polymer, and a terminal-modified polymer having an anchor site to the pigment surface can be cited as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.
Examples of the polymer compound include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA (all are trade names), and the like. Examples of the graft polymer include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” (all trade names) manufactured by BYK Chemie, and the like. It is done.
Examples of the terminal-modified polymer include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol (all are trade names).

  Examples of pigment dispersants other than those that can be preferably used in the present invention include polymer dispersants represented by the following general formula (1).

〔式中、Ｒ^１は、（ｍ＋ｎ）価の連結基を表し、Ｒ^２は単結合あるいは２価の連結基を表す。Ａ^１は、酸性基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、および水酸基からなる群より選ばれる基を有する１価の有機基、または置換基を有してもよい有機色素構造もしくは複素環を含有する１価の有機基を表す。ただし、ｎ個のＡ１は互いに同一であっても、異なっていてもよい。ｍは１〜８の数を表し、ｎは２〜９の数を表し、ｍ＋ｎは３〜１０を満たす。Ｐ^１は高分子骨格を表す。〕

[Wherein, R ¹ represents a (m + n) -valent linking group, and R ² represents a single bond or a divalent linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, n pieces of A1 may be the same as or different from each other. m represents a number of 1 to 8, n represents a number of 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. ]

  The polymer dispersant is more preferably one represented by the following general formula (2).

〔式中、Ｒ^３は、（ｘ＋ｙ）価の連結基を表す。Ｒ^４およびＲ^５は、各々独立に単結合または２価の連結基を表す。Ａ^２は、酸性基、塩基性窒素原子を有する基、ウレア基、ウレタン基、配位性酸素原子を有する基、炭素数４以上の炭化水素基、アルコキシシリル基、エポキシ基、イソシアネート基、および水酸基からなる群より選ばれる基を有する１価の有機基、または置換基を有してもよい有機色素構造もしくは複素環を含有する１価の有機基を表す。ただし、ｘ個のＡ^２は互いに同一であっても、異なっていてもよい。ｙは１〜８の数を表し、ｘは２〜９の数を表し、ｘ＋ｙは３〜１０を満たす。Ｐ^２は高分子骨格を表す。〕

[Wherein R ³ represents a (x + y) -valent linking group. R ⁴ and R ⁵ each independently represents a single bond or a divalent linking group. A ² is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, and A monovalent organic group having a group selected from the group consisting of a hydroxyl group, or a monovalent organic group containing an organic dye structure or a heterocyclic ring which may have a substituent. However, x A ² may be the same or different. y represents a number of 1 to 8, x represents a number of 2 to 9, and x + y satisfies 3 to 10. P ² represents a polymer skeleton. ]

Further, A ¹ or A ² is a monovalent organic group having a group selected from the group consisting of an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. Preferably, the polymer skeleton represented by P ¹ or P ² is a polymer or copolymer of a vinyl monomer, an ester compound polymer, an ether compound polymer, a urethane compound polymer, an amide compound polymer, an epoxy compound polymer, More preferably, it is derived from at least one selected from the group consisting of silicone compound polymers, and modified products and copolymers thereof.

  Specific examples of the polymer dispersant include a pigment dispersant having a graft group described in JP-A-2007-262378 [0077] to [0111], and a general formula (1) described in JP-A 2007-262378 [0140] to [0231]. A nitrogen-containing polymer compound described in JP-A-2007-23169 [0021], and a polymer compound having an acidic group described in the publications [0050] to [0051].

  There are no particular restrictions on the method of introducing these pigment dispersants into the pigment substance dispersion, and a method of dissolving in a good solvent together with an organic pigment, a method of adding to a poor solvent, contact with a good solvent and a poor solvent simultaneously or sequentially. A method of mixing a pigment dispersant solution dissolved separately from these, a method of adding the pigment substance of the present invention when dispersing in a third solvent, and the like can be preferably used.

  In the present invention, the pigment derivative (hereinafter also referred to as “pigment derivative type dispersant”) is derived from an organic pigment as a parent substance, and is manufactured by chemically modifying the parent structure, or It is defined as a pigment derivative type dispersant obtained by a pigmentation reaction of a chemically modified pigment precursor. Generally, it is also called a synergist type dispersant.

  Although not particularly limited, for example, a functional group such as a pigment derivative having an acidic group, a pigment derivative having a basic group, or a phthalimidomethyl group described in JP-A-2007-9096, JP-A-7-331182, or the like. The introduced pigment derivative is preferably used.

Examples of commercially available products include “EFKA 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)” manufactured by EFKA, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative)” manufactured by Lubrizol (any) Product name).
Examples of the linear polymer include an alkali-soluble resin described later, and it is also preferable to use the linear polymer in combination with the pigment derivative.

  In the dye dispersion of the present invention, the dispersant that coexists with the organic pigment fine particles may be used alone or in combination of two or more, and is represented by the above general formula (I). Considering the function of the compound as a dispersion aid, it is preferable to use a combination that can suitably draw out the interaction. The content of the dispersant in the coloring matter or dispersion thereof of the present invention is not particularly limited, but is preferably 5 to 1000 parts by mass, and 10 to 300 parts by mass with respect to 100 parts by mass of the organic pigment. Is more preferable. It is preferable that it is 10-10000 mass parts with respect to 100 mass parts of compounds represented by general formula (I), and it is more preferable that it is 50-1000 mass parts.

  The coloring matter substance and the coloring matter dispersion of the present invention can be used in a photocurable composition. The photocurable composition preferably contains the pigment dispersion, a photopolymerizable compound, and a photopolymerization initiator (hereinafter sometimes referred to as a photopolymerization initiator system), and further includes an alkali-soluble resin. It is more preferable to contain. Hereinafter, each component of the photocurable composition will be described.

  The dye substance and the method for preparing the dispersion have already been described in detail. The content of the organic pigment fine particles in the photocurable composition is preferably 3 to 90% by mass with respect to the total solid content (in the present invention, the total solid content refers to the total composition excluding the organic solvent). 20-80 mass% is more preferable, and 25-60 mass% is further more preferable. If this amount is too large, the viscosity of the dispersion increases, which may cause problems in production suitability. If the amount is too small, coloring power is not sufficient. Moreover, you may use it in combination with a normal pigment for toning. As the pigment, those described above can be used.

  The photopolymerizable compound (hereinafter sometimes referred to as a polymerizable monomer or a polymerizable oligomer) is a polyfunctional monomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. Is preferred. Examples of such a photopolymerizable compound include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned. Further, as described in JP-A-10-62986, general formulas (1) and (2), a compound obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also suitable. As mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

  The photopolymerizable compound may be used alone or in combination of two or more. The content of the photocurable composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. Is preferred. If this amount is too large, it becomes difficult to control the developability, which causes a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

  US Pat. No. 2,367,660 discloses a photopolymerization initiator or a photopolymerization initiator system (a polymerization initiator system refers to a mixture that exhibits a photopolymerization initiation function by a combination of a plurality of compounds). Vicinal polyketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, α-hydrocarbon substituted aromatic acyloin compounds described in US Pat. No. 2,722,512, Polynuclear quinone compounds described in Japanese Patent Nos. 3046127 and 2951758, combinations of triarylimidazole dimers and p-amino ketones described in US Pat. No. 3,549,367, Japanese Patent Publication No. 51-48516 Benzothiazole compounds and trihalomethyl-s-triazine compounds described in US Pat. Trihalomethyl described in 239850 Pat - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.

  In addition, “polymerization initiator C” described in JP-A-11-133600, oxime-based compounds such as 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O— Benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenylcarbonyl-diphenyl phosphonyl oxide, hexafluorophospho-trialkylphenyl phosphonium salt and the like may be mentioned as suitable ones. it can.

  The photopolymerization initiator or the photopolymerization initiator system may be used alone or in combination of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced. The content of the photopolymerization initiator or the photopolymerization initiator system with respect to the total solid content of the photocurable composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass. If this amount is too large, the sensitivity becomes too high and control becomes difficult. If the amount is too small, the exposure sensitivity becomes too low.

  The alkali-soluble resin can be added at the time of preparing the photocurable composition or the inkjet ink for the color filter, but is added when the dispersion composition of the organic pigment fine particles is produced or when the organic pigment fine particles are formed. Is also preferable. An alkali-soluble resin can also be added to both or one of the second solvent for adding the organic pigment solution and the organic pigment solution to form organic pigment fine particles. Alternatively, it is also preferable to add an alkali-soluble resin solution in a separate system when forming organic pigment fine particles.

  As the alkali-soluble resin, a binder having an acidic group is preferable, and an alkali-soluble polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain is preferable. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group, carboxylate, etc. in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers.

  The alkali-soluble resin may be used alone or may be used in the state of a composition used in combination with a normal film-forming polymer. The amount added to 100 parts by mass of the organic pigment fine particles is 10 to 200 parts by mass. Generally, 25-100 mass parts is preferable.

  In addition, in order to improve the crosslinking efficiency, the side chain of the alkali-soluble resin may have a polymerizable group, and a UV curable resin, a thermosetting resin, or the like is also useful. Furthermore, as the alkali-soluble resin, a resin having a water-soluble atomic group in a part of the side chain can be used.

In the photocurable composition, an organic solvent (fourth solvent) for preparing the photocurable composition may be used in addition to the above components. Examples of the fourth solvent include, but are not limited to, alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, amide solvents, aromatic hydrocarbon solvents, aliphatic hydrocarbons. Preferable examples include a system solvent, a nitrile solvent, or a mixture thereof. Among them, a ketone solvent, an ether solvent, an ester solvent, an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or these More preferably, a mixture of
Examples of the ketone solvent include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone and the like. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate. Examples of the ester solvent include 1,3-butylene glycol diacetate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, ethyl Examples thereof include carbitol acetate and butyl carbitol acetate. Examples of the aromatic hydrocarbon solvent include toluene and xylene. Examples of the aliphatic hydrocarbon solvent include cyclohexane and n-octane.
These solvents may be used alone or in combination of two or more. Moreover, the solvent whose boiling point is 180 to 250 degreeC can be used if needed. As for content of an organic solvent, 10-95 mass% is preferable with respect to photocurable composition whole quantity.

  Moreover, it is preferable to contain an appropriate surfactant in the photocurable composition. Suitable surfactants include those disclosed in JP-A Nos. 2003-337424 and 11-133600. As for content of surfactant, 5 mass% or less is preferable with respect to photocurable composition whole quantity.

  The photocurable composition preferably contains a thermal polymerization inhibitor. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl). -6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like. The content of the thermal polymerization inhibitor is preferably 1% by mass or less with respect to the total amount of the photocurable composition.

  In addition to the colorant (pigment), a colorant (dye, pigment) can be added to the photocurable composition as necessary. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the photocurable composition. Specific examples of the dye or pigment include the colorant described in JP-A-2005-17716 [0038] to [0040] and JP-A-2005-361447 [0068] to [0072]. And the colorants described in JP-A-2005-17521 [0080] to [0088] can be suitably used. The auxiliary dye or pigment content is preferably 5% by mass or less based on the total amount of the photocurable composition.

  The photocurable composition can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include salicylate-based, benzophenone-based, benzotriazole-based, cyanoacrylate-based, nickel chelate-based, hindered amine-based compounds and the like in addition to the compounds described in JP-A-5-72724. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the photocurable composition whole quantity.

  In addition to the above additives, the photocurable composition may contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like.

The above-mentioned photocurable composition using the coloring matter substance or coloring matter dispersion of the present invention can be adjusted to an appropriate composition to obtain an inkjet ink. In addition to the color filter, the inkjet ink may be a normal inkjet ink such as for printing, but among them, the inkjet ink for the color filter is preferable.
The ink-jet ink using the pigment substance or pigment dispersion of the present invention may be any ink as long as it contains the organic pigment fine particles, and the medium containing the polymerizable monomer and / or polymerizable oligomer contains the organic pigment fine particles. It is a thing. Here, as the polymerizable monomer and / or polymerizable oligomer, those described above for the photocurable composition can be used.
At this time, it is preferable to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. The viscosity at the time of injection is preferably 5 to 25 mPa · s, more preferably 8 to 22 mPa · s, and particularly preferably 10 to 20 mPa · s (in the present invention, unless otherwise specified) It is a value at 25 ° C.). In addition to the setting of the injection temperature, the viscosity can be adjusted by adjusting the type and amount of components contained in the ink. The viscosity can be measured, for example, by a normal apparatus such as a conical plate type rotational viscometer or an E type viscometer.
The surface tension of the ink upon ejection is preferably 15 to 40 mN / m from the viewpoint of improving the flatness of the pixel (in the present invention, the surface tension is a value at 23 ° C. unless otherwise specified). ). More preferably, it is 20-35 mN / m, Most preferably, it is 25-30 mN / m. The surface tension can be adjusted by adding a surfactant or the type of solvent. For example, the surface tension is platinum by using a measuring instrument such as a surface tension measuring device (CBVP-Z, manufactured by Kyowa Interface Science Co., Ltd.) or a fully automatic balanced electro surface tension meter ESB-V (manufactured by Kyowa Scientific Co., Ltd.). It can be measured by the plate method.

Ink jet ink for color filters can be sprayed by continuously ejecting charged ink and controlled by an electric field, intermittently ejecting ink using piezoelectric elements, or intermittently using ink by heating and foaming. Various methods such as a method of spraying can be employed.
In addition, regarding the ink jet method used for forming each pixel, a normal method such as a method of thermally curing ink, a method of photocuring, or a method of ejecting droplets after forming a transparent image receiving layer on a substrate in advance. Can be used.

  As the ink jet head (hereinafter also simply referred to as a head), a normal one can be applied, and a continuous type and a dot on demand type can be used. Among the dot-on-demand types, the thermal head is preferably a type having an operation valve as described in JP-A-9-323420 for discharging. As the piezo head, for example, the heads described in European Patent A277,703, European Patent A278,590 and the like can be used. The head preferably has a temperature control function so that the temperature of the ink can be controlled. It is preferable to set the injection temperature so that the viscosity at the time of ejection is 5 to 25 mPa · s, and to control the ink temperature so that the fluctuation range of the viscosity is within ± 5%. Moreover, as a drive frequency, it is preferable to operate | move at 1-500 kHz.

In addition, after each pixel is formed, a heating step of performing heat treatment (so-called baking treatment) can be provided. That is, a substrate having a layer photopolymerized by light irradiation is heated in an electric furnace, a dryer or the like, or an infrared lamp is irradiated. The heating temperature and time depend on the composition of the photosensitive dark color composition and the thickness of the formed layer, but generally from about 120 ° C. to obtain sufficient solvent resistance, alkali resistance, and ultraviolet absorbance. Heating at about 250 ° C. for about 10 minutes to about 120 minutes is preferred.
The pattern shape of the color filter thus formed is not particularly limited, and may be a general black matrix stripe shape, a lattice shape, or a delta arrangement. May be.

  In the case of using the pigment substance or pigment dispersion of the present invention, before the pixel formation step using the color filter inkjet ink described above, a partition is created in advance, and the ink is applied to the portion surrounded by the partition The method is preferred. Any partition may be used, but in the case of manufacturing a color filter, it is preferably a light-blocking partition having a black matrix function (hereinafter also simply referred to as “partition”). The partition wall can be produced by the same material and method as those of a normal color filter black matrix. For example, paragraph numbers [0021] to [0074] of JP 2005-3861 A, black matrices described in paragraph numbers [0012] to [0021] of JP 2004-240039 A, and JP 2006-17980 A. And the inkjet black matrix described in paragraphs [0009] to [0044] of JP-A-2006-10875.

  The components contained in the coating film using the photocurable composition are the same as those already described. Moreover, although the thickness of the coating film using a photocurable composition can be suitably determined with the use, it is preferable that it is 0.5-5.0 micrometers, and it is 1.0-3.0 micrometers. Is more preferable. In the coating film using this photocurable composition, the above-mentioned monomer or oligomer can be polymerized to form a polymerized film of the photocurable composition, and a color filter having the polymerized film can be produced (about production of a color filter) Will be described later.) Polymerization of the photopolymerizable compound can be carried out by allowing a photopolymerization initiator or a photopolymerization initiator system to act upon irradiation with light.

  In addition, although the said coating film can be formed by apply | coating and drying a photocurable composition with a normal application method, it applies with the slit-shaped nozzle which has a slit-shaped hole in the part which discharges a liquid. It is preferable. Specifically, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163. Slit nozzles and slit coaters described in Japanese Patent Laid-Open No. 2001-310147 and the like are preferably used.

  As a method for applying the photocurable composition to the substrate, spin coating is excellent in that a thin film having a thickness of 1 to 3 μm can be uniformly and highly accurately applied, and can be widely used for producing color filters. However, in recent years, with the increase in size and mass production of liquid crystal display devices, slit coating suitable for coating a substrate that is wider and larger in area than spin coating has been used in order to increase manufacturing efficiency and manufacturing cost. It has come to be adopted in the production of. From the viewpoint of liquid-saving properties, slit coating is superior to spin coating, and a uniform coating film can be obtained with a smaller amount of coating liquid.

  In slit coating, a coating head having a slit (gap) with a width of several tens of microns at the tip and a length corresponding to the coating width of a rectangular substrate is maintained at a clearance (gap) of several tens to several hundreds of microns with the substrate. On the other hand, this is a coating method in which a coating liquid supplied from a slit is applied to a substrate with a predetermined discharge amount by giving a constant relative speed between the substrate and the coating head. This slit coating is (1) less liquid loss compared to spin coating, (2) cleaning process is reduced because there is no flying of the coating liquid, and (3) the scattered liquid components are applied to the coating film again. There is an advantage that there is no mixing, (4) the tact time can be shortened because there is no start-up stop time of rotation, and (5) application to a large substrate is easy. From these advantages, slit coating is suitable for producing a color filter for a large-screen liquid crystal display device, and is expected as an advantageous coating method for reducing the amount of coating liquid.

  The coating in the above production method can be performed by a normal coating apparatus or the like. However, in the case of using the pigment substance or pigment dispersion of the present invention, the coating apparatus using the slit-shaped nozzle (slit described above). It is preferable to use a coater. Preferred specific examples of the slit coater are the same as described above.

The color filter using the pigment substance or pigment dispersion of the present invention is excellent in contrast. In the present invention, the contrast represents the ratio of the amount of transmitted light between two polarizing plates when the polarization axis is parallel and when it is vertical (“1990 Seventh Color Optical Conference, 512-color display 10.4. "Refer to" Color TFT for TFT-LCD, Ueki, Koseki, Fukunaga, Yamanaka "etc.).
The high contrast of the color filter means that the bright and dark discrimination when combined with the liquid crystal can be increased, and this is a very important performance in order to replace the liquid crystal display with a CRT.

  When the color filter using the pigment substance or pigment dispersion of the present invention is used for television, the chromaticity of all monochromatic colors of red (R), green (G), and blue (B) by the F10 light source. However, it is preferable that the difference (ΔE) with respect to the value shown in the table below (hereinafter referred to as “target chromaticity” in the present invention) is in the range of 5 or less, more preferably 3 or less. Is particularly preferable.

x y Y
------------------------
R 0.656 0.336 21.4
G 0.293 0.634 52.1
B 0.146 0.088 6.90
------------------------

In the present invention, the chromaticity is measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd .; OSP100 or 200), calculated as a result of the F10 light source field of view of 2 degrees, and expressed as an xyY value in the xyz color system. Further, the difference from the target chromaticity is represented by a color difference of the La ^* b ^* color system.

  A liquid crystal display device provided with a color filter using the pigment substance or pigment dispersion of the present invention has a high contrast and is excellent in descriptive power such as black spots, and is particularly preferably a VA system. It can also be suitably used as a large-screen liquid crystal display device such as a notebook personal computer display or a television monitor. In addition, the color filter using the pigment substance or pigment dispersion of the present invention can be used for a CCD device and exhibits excellent performance.

EXAMPLES Hereinafter, although this invention is demonstrated in more detail based on an Example, this invention is limited to this and is not interpreted.
Example 1
Pigment C.I. to 220 ml of dimethyl sulfoxide at room temperature. I. Pigment Red 254 (trade name Irgazine Red 2030, manufactured by Ciba Specialty Chemicals Co., Ltd.) 11 g, tetramethylammonium hydroxide 25% aqueous solution 14.0 ml, 1.1 g of the exemplified compound P-2 were added and stirred. . Thus, an organic pigment solution in which the pigment was dissolved in a good solvent was obtained.
Separately, 2000 ml of water containing 40 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.

  Here, the temperature of the organic pigment solution was controlled at 5 ° C., and the organic pigment solution was NP-KX-500 in the poor solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). An organic pigment solution and a poor solvent were brought into contact with each other by injecting using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to precipitate organic pigment fine particles. At this time, the injection of the organic pigment solution was carried out at a flow rate of 100 ml / min for 2 minutes at a flow rate of 100 ml / min, with the flow channel diameter and the supply port diameter of the liquid feed pipe set to 0.5 mm. Thus, a pigment dispersion 1-1W in which organic pigment fine particles were dispersed in a solvent was obtained.

  The pigment dispersion prepared by the above procedure is subjected to vacuum filtration with an aspirator using Nutsche and filter paper (Advantech Co., Ltd., No. 2 (trade name)) with a diameter of 9 cm, thereby containing a fine pigment material. Got. By repeating the procedure of dispersing the obtained paste in distilled water and filtering again, the paste was washed with water to remove the good solvent and water-soluble ions. The washing of the paste with water was repeated until the conductivity when the paste was dispersed to a pigment concentration of 5% was 1 μs or less.

  The water paste containing the pigment thus obtained was dried at 80 ° C. for 12 hours to obtain a powdered pigment substance 1-1P containing the pigment and the exemplified compound P-2.

Preparation of Dye Dispersion Dye dispersion 1-1D of the present invention was prepared by bead mill dispersion of a dye substance, a dispersant and a solvent mixture having the following composition.
Dispersion was performed for 5 hours at a peripheral speed of 9 m / s using a motor mill M-50 (trade name, manufactured by Eiger Japan) using zirconia beads having a diameter of 0.1 mm.
11.0 parts by mass of pigment substance 1-1P (10 parts by mass of pigment)
Dispersant C-1 10.0 parts by mass 1-methoxy-2-propyl acetate 79.0 parts by mass

  As a result of observation with an electron microscope, the obtained pigment dispersion 1-1D was confirmed to contain fine pigment particles having a volume weighted average diameter of 20.0 nm (converted to the same volume sphere) and a coefficient of variation of 15%.

<Evaluation>
The following evaluation was performed on the dispersion liquid 1-1D.
(1) Filterability The filtration rate at the time of filtering the pigment dispersion 1-1W by the said method was measured. The following ranking was performed according to the filtration time.
5: A considerably preferable level within a filtration time of 1 minute and 30 seconds.
4: A preferable level at a filtration time of 1 minute 30 seconds to 3 minutes.
3: Acceptable level within 3 to 5 minutes of filtration time.
2: Level of problem within 5 to 10 minutes of filtration time.
1: A considerably problematic level when the filtration time is 10 minutes or more.
(2) Contrast evaluation The obtained pigment dispersion 1-1D was applied on a glass substrate so as to have a thickness of 2 μm, thereby preparing a sample. Using a three-wavelength cold-cathode tube light source (trade name: FWL18EX-N, manufactured by Toshiba Lighting & Technology Corp.) as a backlight unit, two polarizing plates (polarizing plates manufactured by Sanritsu Co., Ltd.) This sample was placed between the product names: HLC2-2518), and the amount of transmitted light was measured when the polarization axis was parallel and when it was vertical, and the contrast was determined from the ratio (“1990 7th Color Optics”). Conference, 512 color display 10.4 "size TFT-LCD color filter, Ueki, Koseki, Fukunaga, Yamanaka" etc.). Two polarizing plates, a sample, and a color luminance meter are installed at a position where the polarizing plate is 13 mm from the backlight, and a cylinder having a diameter of 11 mm and a length of 20 mm is installed at a position of 40 mm to 60 mm. Was measured on a color luminance meter installed at a position of 400 mm through a polarizing plate installed at a position of 100 mm. The measurement angle of the color luminance meter was set to 2 °. The light quantity of the backlight was set so that the luminance when the two polarizing plates were installed in parallel Nicol was 1280 cd / m ² without the sample being installed.
The contrast value obtained by the above was calculated | required as ratio with respect to the value of the below-mentioned dispersion liquid 1-2D, and the following ranking was performed.
6: Contrast ratio 5 times or more 5: Contrast ratio 4 times or more and less than 5 times 4: Contrast ratio 3 times or more and less than 4 times 3: Contrast ratio 2 times or more and less than 3 times 2: Contrast ratio 1.5 times or more and less than 2 times 1 : Contrast ratio less than 1.5 times

  For the method of preparing the dye dispersion 1-1D, the type and amount of the compound added to the good solvent and the type of dispersant used were changed as shown in Table 1, and the bead mill dispersion time was optimized. Only dispersion methods were prepared by different methods to obtain pigment dispersions 1-2D to 1-24D. These dye dispersions were evaluated in the same manner as the dye dispersion 1-1D. The compounds used as dispersants and the compounds used as comparative compounds are shown below.

  The obtained evaluation results are shown in Table 1. From the results in Table 1, the excellent effects of the present invention can be seen. That is, when the compound represented by the general formula (I) is used as a dispersion aid, good filterability and contrast levels are obtained. On the other hand, when a compound having a polar group generally known as a dispersion aid (compounds A, C, D, E, F, G) or a polymer material having high water solubility (compounds B, H) is used. ) Shows that the contrast is improved and the dispersibility is improved. On the other hand, the filterability is deteriorated. In addition, when a polymer compound that is poorly soluble in a poor solvent is used (Compound I), the filterability is hardly deteriorated but the contrast is not improved and the dispersibility is not improved. .

  As a result of observation with an electron microscope, the dye dispersion liquids 1-2D and 1-24D both contain fine pigment particles having a volume-weighted average diameter of about 25 nm (converted to the same volume sphere) and a coefficient of variation of about 15%. confirmed. In addition, it was confirmed that each of the dye dispersions 1-3D to 1-23D contains fine pigment particles having a volume weighted average diameter of about 20 nm (converted to the same volume sphere) and a coefficient of variation of about 15%.

(Example 2)
Pigment C.I. to 220 ml of dimethyl sulfoxide at room temperature. I. 16 g of Pigment Red 122 (product name: Chromophthaljet Magenta DMQ, manufactured by Ciba Japan Co., Ltd.), 47.0 ml of a 25% aqueous solution of tetramethylammonium hydroxide, and 0.16 g of the exemplified compound P-2 were added and stirred. Thus, an organic pigment solution in which the organic pigment was dissolved in a good solvent was obtained.
Separately, 2000 ml of water containing 47 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.

  Here, the temperature of the solution was controlled at 5 ° C., and the pigment solution was added to NP-KX-500 type large capacity in 2000 ml of poor solvent stirred at 500 rpm by GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). 200 ml was injected at a flow rate of 10 ml / min using a non-pulsating pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.). Thus, a pigment dispersion 2-1W containing pigment particles and a solvent was obtained.

  The pigment dispersion prepared in the above procedure is filtered under reduced pressure with an aspirator using Nutsche and filter paper (Advantech Co., No. 2 (trade name)) having a diameter of 9 cm to obtain a paste containing organic pigment fine particles. It was. By repeating the procedure of dispersing the obtained paste in distilled water and filtering again, the paste was washed with water to remove the good solvent and water-soluble ions. The washing of the paste with water was repeated until the conductivity when the paste was dispersed to a pigment concentration of 5% was 1 μs or less.

  The water paste containing the pigment thus obtained was dried at 80 ° C. for 12 hours to obtain a powdered coloring substance 2-1P containing the pigment and the exemplified compound P-2.

Preparation of Dye Dispersion Dye dispersion 2-1D of the present invention was prepared by dispersing a dye substance, a dispersant, and a solvent mixture having the following composition.
Dispersion was performed for 5 hours at a peripheral speed of 9 m / s using a motor mill M-50 (trade name, manufactured by Eiger Japan) using zirconia beads having a diameter of 0.1 mm.
11.0 parts by mass of pigment substance 2-1P (10 parts by mass of pigment)
Dispersant C-1 10.0 parts by mass 1-methoxy-2-propyl acetate 79.0 parts by mass

  As a result of observation with an electron microscope, the obtained pigment dispersion 2-1D was confirmed to contain fine pigment particles having a volume weighted average diameter of 20.0 nm (converted to the same volume sphere) and a coefficient of variation of 15%.

By the method different from the method for preparing the dye dispersion 2-1D, only the type and amount of the compound added in the good solvent are changed as shown in Table 2 and the bead mill dispersion time is optimized. A dispersion was prepared to obtain pigment dispersions 2-2D to 2-6D. These dye dispersions were evaluated in the same manner as in Example 1. Here, the contrast was evaluated as a relative value with respect to the value of the pigment dispersion 2-2D, and the following ranking was performed.
6: Contrast ratio 5 times or more 5: Contrast ratio 4 times or more and less than 5 times 4: Contrast ratio 3 times or more and less than 4 times 3: Contrast ratio 2 times or more and less than 3 times 2: Contrast ratio 1.5 times or more and less than 2 times 1 : Contrast ratio less than 1.5 times

  The obtained evaluation results are shown in Table 2. From the results in Table 2, the excellent effects of the present invention can be seen. That is, when the compound represented by the general formula (I) is used as a dispersion aid, good filterability and contrast levels are obtained. On the other hand, when the compound (A, E) having a polar group, which is generally known as a dispersion aid, is used, the contrast is improved and the dispersibility is improved, but the filterability is deteriorated. I understand that.

  As a result of observation with an electron microscope, it was confirmed that the dye dispersion 2-2D contains fine pigment particles having a volume weighted average diameter of about 25 nm (converted to the same volume sphere) and a coefficient of variation of about 15%. In addition, it was confirmed that each of the pigment dispersions 2-3D to 2-6D contains fine pigment particles having a volume weighted average diameter of about 20 nm (converted to the same volume sphere) and a coefficient of variation of about 15%.

(Example 3)
Pigment C.I. to 220 ml of dimethyl sulfoxide at room temperature. I. Pigment Yellow 185 (trade name, manufactured by PALIOTOL YELLOW D1155 BASF) 11 g, sodium methoxide 28% methanol solution 6.6 ml, and 1.1 g of the exemplified compound P-22 were added and stirred. Thus, an organic pigment solution in which the organic pigment was dissolved in a good solvent was obtained.
Separately, 2000 ml of water containing 37.5 ml of 1 mol / l hydrochloric acid was prepared as a poor solvent.

  Here, the temperature of the organic pigment solution was controlled at 5 ° C., and the organic pigment solution was NP-KX-500 in the poor solvent stirred at 500 rpm with a GK-0222-10 type Lamond Stirrer (trade name, manufactured by Fujisawa Pharmaceutical Co., Ltd.). An organic pigment solution and a poor solvent were brought into contact with each other by injecting using a large-capacity non-pulsating flow pump (trade name, manufactured by Nippon Seimitsu Chemical Co., Ltd.) to precipitate organic pigment fine particles. At this time, the injection of the organic pigment solution was carried out at a flow rate of 100 ml / min for 2 minutes at a flow rate of 100 ml / min, with the flow channel diameter and the supply port diameter of the liquid feed pipe set to 0.5 mm. Thus, a pigment dispersion 3-1W containing organic pigment fine particles and a solvent was obtained.

  The pigment dispersion prepared in the above procedure is filtered under reduced pressure with an aspirator using Nutsche and filter paper (Advantech Co., No. 2 (trade name)) having a diameter of 9 cm to obtain a paste containing organic pigment fine particles. It was. By repeating the procedure of dispersing the obtained paste in distilled water and filtering again, the paste was washed with water to remove the good solvent and water-soluble ions. The washing of the paste with water was repeated until the conductivity when the paste was dispersed to a pigment concentration of 5% was 1 μs or less.

  The water paste containing the pigment thus obtained was dried at 80 ° C. for 12 hours to obtain a powdered coloring material 3-1P containing the pigment and the exemplified compound P-22.

Preparation of pigment dispersion A pigment dispersion 3-1D of the present invention was prepared by dispersing a pigment substance, a dispersant, and a solvent mixture having the following composition.
Dispersion was performed for 5 hours at a peripheral speed of 9 m / s using a motor mill M-50 (trade name, manufactured by Eiger Japan) using zirconia beads having a diameter of 0.1 mm.
11.0 parts by mass of pigment material 3-1P (10 parts by mass of pigment)
Dispersant C-1 10.0 parts by mass 1-methoxy-2-propyl acetate 79.0 parts by mass

  As a result of observation with an electron microscope, the obtained pigment dispersion 3-1D was confirmed to contain fine pigment particles having a volume-weighted average diameter of 23.0 nm (converted to the same volume sphere) and a coefficient of variation of 15%.

Dispersing the dye dispersion 3-1D by a different method except that the type and amount of the compound added to the good solvent are changed as shown in Table 3 and the bead mill dispersion time is optimized. A liquid was prepared to obtain pigment dispersions 3-2D to 3-6D. These dye dispersions were evaluated in the same manner as in Example 1. Here, the contrast was evaluated as a relative value with respect to the value of the dye dispersion 3-1D, and the following ranking was performed.
5: Contrast ratio 4 times to less than 5 times 4: Contrast ratio 3 times to less than 4 times 3: Contrast ratio 2 times to less than 3 times 2: Contrast ratio 1.5 times to less than 2 times 1: Contrast ratio 1.5 times Less than

  The obtained evaluation results are shown in Table 3. From the results of Table 3, the excellent effects of the present invention can be seen. That is, when the compound represented by the general formula (I) is used as a dispersion aid, good filterability and contrast levels are obtained. On the other hand, when the compound (A, D) having a polar group, which is generally known as a dispersion aid, is used, the contrast is improved and the dispersibility is improved, but the filterability is deteriorated. I understand that.

  As a result of observation with an electron microscope, it was confirmed that the pigment dispersion 3-2D contains fine pigment particles having a volume weighted average diameter of about 30 nm (converted to the same volume sphere) and a coefficient of variation of about 15%. In addition, it was confirmed that each of the pigment dispersions 3-3D to 3-6D contains fine pigment particles having a volume weighted average diameter of about 23 nm (converted to the same volume sphere) and a coefficient of variation of about 15%.

Example 4
A dispersion liquid was prepared by a method different from the preparation method of the dye dispersion liquid 1-2D of Example 1 only in that a dispersion aid was added as shown in Table 4 at the time of dispersion using a bead mill. 4-1D to 4-5D were obtained. Here, the dispersion aid was added in a dry powder state. Moreover, the drying method in the middle and the addition method of a dispersing agent and a dispersing aid are changed with respect to the preparation method of the pigment dispersion 4-1D, and the pigment paste before drying, the dispersing aid P-3, and the dispersing agent C- 1 is dispersed with a dissolver together with acetone and 1-methoxy-2-propyl acetate, and then a paste from which water and acetone are removed by decompression is prepared, and the obtained paste is dispersed by a bead mill dispersion without drying. A liquid was prepared to obtain a pigment dispersion 4-6D. Further, a dispersion liquid was prepared by a method different from the preparation method of the dye dispersion liquid 4-6D only in that the dispersion auxiliary agent P-4 was not added, and a dye dispersion liquid 4-7D was obtained.
When the contrast of these dispersions was determined in the same manner as in Example 1, it was shown that the contrast was improved, and that the specific dispersion aid in the present invention was effective even when the addition timing was changed.

(Example 5)
<Create color filter>
As a result of producing a color filter by the following procedure using the dye dispersion liquid 2-1D obtained in Example 2, a good contrast is obtained as a color filter, and the dye dispersion liquid of the present invention is suitably used for the color filter. I confirmed that I can do it.

[Formation of black (K) image]
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat-treated at 120 ° C. for 3 minutes to stabilize the surface state.
After cooling the substrate and adjusting the temperature to 23 ° C., the composition described in Table 5 below is applied on a glass substrate coater (manufactured by FS Asia Co., Ltd., trade name: MH-1600) having a slit-like nozzle. A colored photosensitive resin composition K1 was applied. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive resin layer K1 was obtained.

[Table 5]
--------------------------------------
K pigment dispersion 1 (carbon black) 25 parts by mass Propylene glycol monomethyl ether acetate 8.0 parts by mass Methyl ethyl ketone 53 parts by mass Binder 2 9.1 parts by mass Hydroquinone monomethyl ether 0.002 parts by mass DPHA solution 4.2 parts by mass Polymerization start Agent A 0.16 parts by mass Surfactant 1 0.044 parts by mass -------------------------------- ------

In a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the mask The distance between the photosensitive resin layers was set to 200 μm, and pattern exposure was performed at an exposure amount of 300 mJ / cm ² .
Next, after spraying pure water with a shower nozzle to uniformly wet the surface of the photosensitive resin layer K1, a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials, Inc., 100-fold diluted solution) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove the residue, and a black (K) image K was obtained. Subsequently, heat treatment was performed at 220 ° C. for 30 minutes.

  For the colored photosensitive resin composition K1, first, K pigment dispersion 1 and propylene glycol monomethyl ether acetate are weighed, mixed at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 10 minutes, and then methyl ethyl ketone, binder 2 , Hydroquinone monomethyl ether, DPHA solution, polymerization initiator A (2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethyl) amino-3'-bromophenyl] -s- Triazine) and surfactant 1 were weighed out, added in this order at a temperature of 25 ° C. (± 2 ° C.), and stirred at 150 rpm for 30 minutes at a temperature of 40 ° C. (± 2 ° C.).

<K pigment dispersion 1>
・ Carbon black (trade name: Nipex 35, manufactured by Degussa Japan)
13.1 parts by mass / dispersant (compound J1) 0.65 parts by mass / polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio
Random copolymer of, molecular weight 37,000) 6.72 parts by mass / propylene glycol monomethyl ether acetate 79.53 parts by mass

<Binder 2>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
27 parts by mass / propylene glycol monomethyl ether acetate 73 parts by mass <Surfactant 1>
MegaFuck F-780-F (trade name: Dainippon Ink & Chemicals, Inc.)
: The composition is as follows: C ₆ F ₁₃ CH ₂ CH ₂ OCOCH = CH ₂ 40 parts by mass and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH = CH ₂ 55 parts by mass and H (OCH ₂ CH ₂ ) ₇ OCOCH = Copolymer with 5 parts by mass of CH ₂ (molecular weight 30,000)
30 parts by mass, 70 parts by mass of methyl ethyl ketone

[Formation of red (R) pixels]
A heat-treated pixel R was formed on the substrate on which the image K was formed using the colored photosensitive resin composition R1 having the composition shown in Table 6 below in the same process as the formation of the black (K) image. The film thickness of the photosensitive resin layer R1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment coating amount (g / m ² ) 1.00
C. I. P. R. 122 coating amount (g / m ² ) 0.80
C. I. P. R. 177 coating amount (g / m ² ) 0.20

[Table 6]
--------------------------------------
R pigment dispersion 2-1D 40 parts by mass R pigment dispersion 2 (CIPR177) 4.5 parts by mass Propylene glycol monomethyl ether acetate 7.6 parts by mass Methyl ethyl ketone 37 parts by mass Binder 1 0.7 parts by mass DPHA liquid 3.8 parts by mass Part 2-Trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 1 0.06 parts by mass ----------- --------------------------

<R pigment dispersion 2>
・ C. I. P. R. 177 (Product name: Chromophthal Red A2B,
Ciba Specialty Chemicals Co., Ltd.) 18 parts by mass Polymer (benzyl methacrylate / methacrylic acid = 72/28 molar ratio)
Random copolymer of, molecular weight 30,000) 12 parts by mass / 70 parts by mass of propylene glycol monomethyl ether acetate <Binder 1>
・ Polymer (benzyl methacrylate / methacrylic acid = 78/22 molar ratio
Random copolymer of, molecular weight 40,000) 27 parts by mass, propylene glycol monomethyl ether acetate 73 parts by mass

[Formation of green (G) pixels]
Using the colored photosensitive resin composition G1 having the composition shown in Table 7 below on the substrate on which the image K and the pixel R are formed, the heat-treated pixel G is formed in the same process as the formation of the black (K) image. Formed. The film thickness of the photosensitive resin layer G1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 1.92
C. I. P. G. 36 coating amount (g / m ² ) 1.34
C. I. P. Y. 150 coating amount (g / m ² ) 0.58

[Table 7]
--------------------------------------
G pigment dispersion 1 (CIPG 36) 28 parts by mass Y pigment dispersion 1 (CIPI 150) 15 parts by mass Propylene glycol monomethyl ether acetate 29 parts by mass Methyl ethyl ketone 26 parts by mass Cyclohexanone 1.3 parts by mass Binder 2 2.5 parts by mass DPHA solution 3 0.5 part by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.12 parts by mass Polymerization initiator A 0.05 parts by mass Phenothiazine 0.01 parts by mass Surfactant 1 0.07 parts by mass ----------- --------------------------

<G pigment dispersion 1>
GT-2 (trade name: manufactured by FUJIFILM Electronics Materials)
<Y pigment dispersion 1>
CF yellow-EX3393 (trade name: manufactured by Mikuni Color Co., Ltd.)

[Formation of blue (B) pixels]
Using the colored photosensitive resin composition B1 having the composition shown in Table 8 below on the substrate on which the image K, the pixel R, and the pixel G are formed, heat treatment is performed in the same process as the formation of the black (K) image. Pixel B was formed. The film thickness of the photosensitive resin layer B1 and the coating amount of the pigment are shown below. In addition, the preparation procedure of the colored photosensitive resin composition was the same as that of the colored photosensitive resin composition K1.
Photosensitive resin film thickness (μm) 1.60
Pigment application amount (g / m ² ) 0.75
C. I. P. B. 15: 6 coating amount (g / m ² ) 0.705
C. I. P. V. 23 coating amount (g / m ² ) 0.045

[Table 8]
--------------------------------------
B pigment dispersion 1 (CIPB15: 6) 8.6 parts by mass V pigment dispersion 2 (CIPB15: 6 + CIPV23) 15 parts by mass Propylene glycol monomethyl ether acetate 28 parts by mass Methyl ethyl ketone 26 parts by mass Binder 3 17 parts by mass DPHA solution 4.0 Parts by mass 2-trichloromethyl- (p-styrylstyryl)
1,3,4-oxadiazole 0.17 parts by mass Phenothiazine 0.02 parts by mass Surfactant 0.06 parts by mass -------------------- -----------------

<B pigment dispersion 1>
CF Bull-EX3357 (trade name: manufactured by Mikuni Color Co., Ltd.)
<B pigment dispersion 2>
CF Bull-EX3383 (trade name: manufactured by Mikuni Color Co., Ltd.)
<Binder 3>
・ Polymer (benzyl methacrylate / methacrylic acid / methyl methacrylate = 36/22/42 molar ratio random copolymer, molecular weight 38,000) 27 parts by mass-propylene glycol monomethyl ether acetate 73 parts by mass

[Production of ITO electrodes]
The glass substrate on which each pixel is formed is put into a sputtering apparatus, and 1300 mm thick ITO (indium tin oxide) is vacuum-deposited on the entire surface at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO. A transparent electrode was formed to complete the color filter A1.

Claims (7)

A fine pigment substance comprising organic pigment fine particles obtained by precipitation by contact between an organic pigment solution dissolved in a good solvent and a poor solvent, and a compound represented by the following general formula (I):
Formula (I)
P- (XR) n
(Wherein P is an organic dye structure residue or heterocyclic residue which may have a substituent, X is a direct bond or a divalent linking group, R is an aliphatic hydrocarbon group having 3 to 30 carbon atoms, (Represents any group of an aryl group, an aralkyl group and an oxyalkylene group, and n represents an integer of 1 to 4).   2. The coloring matter substance according to claim 1, wherein the organic pigment fine particles are precipitated in the presence of the compound represented by the general formula (I).   The coloring matter substance according to claim 1, wherein the mixing of the organic pigment fine particles and the compound represented by the general formula (I) is performed after the precipitation of the organic pigment fine particles.   The coloring matter substance according to any one of claims 1 to 3, wherein at least a part of the good solvent is removed after the organic pigment fine particles are deposited. The coloring matter substance according to any one of claims 1 to 4, wherein the compound represented by the general formula (I) is represented by the following general formula (I)-(1).

(In the formula, R ¹ represents an aliphatic hydrocarbon group having 3 to 30 carbon atoms, an aryl group, an aralkyl group or an oxyalkylene group. R ² , R ³ , R ⁴ and R ⁵ are each independently selected. Represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, or a cyano group.)   A pigment substance dispersion comprising the pigment substance according to claim 1 and a dispersion solvent having a composition different from that of the good solvent.   The dispersion solvent is substantially composed of at least one selected from the group consisting of ether solvents, ester solvents, ketone solvents, aromatic hydrocarbon solvents, and aliphatic hydrocarbon solvents. The pigment substance dispersion according to claim 6.