JP2007191559A - Azo pigment, organic nanoparticle dispersed composition and color filter using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azo pigment, a composition where organic nanoparticles are dispersed and a color filter using the same having a clear tint, high coloring ability and high weather resistance. <P>SOLUTION: The azo pigment is shown by general formula (1) wherein R<SP>1</SP>is a hydrogen atom, an alkyl group or an aryl group and A is a hetero ring forming a 5- or 6-membered ring. The nanoparticles dispersed composition is prepared by mixing a solution where the pigment is dispersed in at least one good solvent for the pigment with a poor solvent compatible with the above solvent in the presence of a binder containing an acid group which is soluble in an alkaline material, followed by concentrating, whereby the organic nanoparticle dispersed composition wherein thus-produced organic nano particles having a particle size of 1 μm or less are dispersed. The color filter comprises colored photo-sensitive resin composition containing the pigment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel azo dye, an organic nanoparticle dispersion composition, a colored photosensitive resin composition, and a color filter having a clear color tone, high coloring degree, weather resistance, and high contrast.

  Conventionally, pigments have a clear color tone, high tinting strength, and weather resistance, and have been widely used in many fields. Among these pigments, those that are practically important are generally those of fine particles, and a clear color tone and high coloring power can be obtained by preventing the pigment from agglomerating and making it finer. However, when the pigment is further refined by a physical method such as salt milling, the viscosity of the pigment dispersion often increases. For this reason, when preparing a pigment dispersion on an industrial scale, it is difficult to take out from the disperser, it cannot be transported by a pipeline, or it becomes gelled during storage and becomes unusable. was there.

  Therefore, in order to obtain a pigment dispersion or colored photosensitive composition having excellent fluidity and dispersibility, surface treatment of organic pigments has been carried out (for example, see Patent Documents 1 and 2), and various dispersants have been used. Attempts have been made (see, for example, Patent Documents 3 and 4). Further, a reprecipitation method is disclosed in which particles are formed by injecting a sample dissolved in a good solvent into a poor solvent whose stirring conditions and temperature are controlled (see, for example, Patent Document 5).

  On the other hand, when a colored image is formed using the colored photosensitive composition, generally, a coating solution of the colored photosensitive composition is applied onto a substrate to form a layer of the composition, and then exposure and development are performed. . An alkaline aqueous solution having little influence on the environment is often used as a developer used in the development, but it is required that the developer can be developed with the alkaline aqueous solution. On the other hand, the solvent (pigment dispersion medium) used in the coating solution of the colored photosensitive composition is also required to be easy to dry after coating. Furthermore, since the layer made of such a colored photosensitive composition is generally required to be extremely thin and to exhibit a high color density, for example, in an organic solvent, an organic pigment is highly concentrated and uniformly miniaturized. It is necessary to disperse in such a state.

A pigment dispersion that satisfies these requirements and has excellent dispersibility and fluidity of the pigment, a pigment dispersion composition containing the pigment dispersion, and a colored photosensitive composition cannot be obtained by the conventional methods as described above. The current situation is not yet provided. Among these, as for yellow pigments, nickel complexes such as P.Y.150 and P.Y.185 are widely known, but P.Y.150 is required to improve the influence on the environment. As for .185, the solubility as a pigment is too high, which causes a problem in the fine particle dispersion process.
With regard to the solubility of the pigment, it is possible to consider increasing the molecular weight if it is only slightly soluble, but for example, conventional bis-type isoindoline pigments have difficulty in synthesis and cannot guarantee purity (Patent Document 6). ). Therefore, development of a new dye skeleton is necessary, but azo dyes combined with aniline couplers are known as naphthalimide diazo component dyes (Reference 7), but yellow azo dyes combined with heterocyclic couplers are completely different. It was not known.
JP-A-11-269401 Japanese Patent Laid-Open No. 11-302553 JP-A-8-48890 JP 2000-239554 A JP 2004-123853 A Japanese Patent Laid-Open No. 55-3490 Dyes and Pigments 7 (1986) 237-247

  An object of the present invention is to provide a novel azo dye, an organic nanoparticle dispersion composition, and a color filter using the same, and in particular, a color filter exhibiting a vivid color tone, high coloring degree, weather resistance, and high contrast. To do.

The above problems have been achieved by the following means.
(1) An azo dye represented by the following general formula (1).

In general formula (1), R ¹ represents a hydrogen atom, an alkyl group, or an aryl group, and A represents a heterocyclic group that forms a 5-membered or 6-membered ring.
(2) An azo dye wherein A is a heterocyclic group represented by the following general formula (2), (3) or (4).

In the general formulas (2), (3), and (4), * represents a bonding site with an N atom, and R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom, a cyano group,- CONH _{2 represents} an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.
(3) A solution in which at least one azo dye represented by the general formula (1) is dissolved in a good solvent, and a poor solvent compatible with the solvent, in the presence of an alkali-soluble binder having an acidic group. An organic nanoparticle-dispersed composition, characterized by being mixed to form a mixed solution in which the dye is produced as organic nanoparticles having a particle size of 1 μm or less.
(4) The organic nanoparticle composition according to (3), wherein the mixed solution is concentrated and / or desalted.
(5) (I) An alkali-soluble binder having an acidic group (a solution obtained by dissolving at least one azo dye represented by the general formula (1) in a good solvent and a poor solvent compatible with the solvent) A mixed solution prepared by mixing in the presence of A) to produce the dye as organic nanoparticles having a particle size of 1 μm or less, and (II) an alkali-soluble binder having an acidic group (B) [where (A) and ( B) may be the same or different], and (III) a colored photosensitive resin composition containing at least a monomer or oligomer and (IV) a photopolymerization initiator or photopolymerization initiator system. A color filter comprising a colored photosensitive polymer obtained by polymerizing a polymerizable component in the composition.

  The azo dye of the present invention has high colorability. In addition, the organic nanoparticle dispersion composition of the present invention disperses the organic nanoparticles contained therein in a highly uniform and miniaturized state, and therefore can exhibit a high coloring density with a thin film thickness. . In addition, the color filter of the present invention exhibits high contrast and light resistance, is excellent in descriptive power such as black spots, and can be suitably used for a liquid crystal display device or the like.

  In the present invention, a novel azo dye, a solution obtained by dissolving the azo dye in a good solvent, and a poor solvent that is compatible with the good solvent are mixed to produce the pigment as organic nanoparticles. The present invention relates to a well-concentrated organic nanoparticle dispersion composition, and also relates to a dispersion composition obtained by remixing organic nanoparticles by mixing a mixed solution in which organic nanoparticles are generated and an alkali-soluble binder having an acidic group. These dispersion compositions have small changes in the size and monodispersity of the organic nanoparticles in the concentration step, preferably do not change, and can be redispersed even when the organic nanoparticles aggregate due to concentration. . Therefore, the organic nanoparticles in the dispersion composition are excellent in monodispersity and sufficiently fine, and are excellent as a colored photosensitive resin composition for a color filter. Color filters, liquid crystal display devices, and the like having the same can exhibit high performance. Is. Hereinafter, the present invention will be described in detail.

[Organic materials]
The azo dye of the present invention is a dye represented by the following general formula (1).
Moreover, in the organic nanoparticle dispersion composition of this invention, the azo pigment | dye represented by following General formula (1) is used as an organic material which forms the organic nanoparticle contained therein.

In the general formula (1), R ¹ represents a hydrogen atom, an alkyl group, or an aryl group. A represents a heterocyclic group forming a 5-membered or 6-membered ring, and may be a monocyclic structure or a polycyclic structure in which two or more rings are condensed. A is preferably a heterocyclic group containing at least one of N, O, and S. As the heterocyclic ring, a pyridine ring, pyrazine ring, pyrimidine ring, pyridone ring, pyrazolopyridone ring which may have a substituent may be used. Pyrrole ring, pyrazole ring, pyrazolotriazole ring, pyrrolotriazole ring, furan ring, thiophene ring, barbitur ring, thiobarbitur ring and the like. A is more preferably a heterocyclic group represented by any one of the following general formulas (2) to (4).

In the general formulas (2), (3) and (4), R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a cyano group, —CONH _{2 represents} an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.

In the general formulas (1) to (4), the alkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ includes an alkyl group having a substituent and an alkyl group having no substituent. Substituted alkyl groups are included. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms. Examples of the substituent include a hydroxyl group, an alkoxy group, a cyano group, a halogen atom and the like. Examples of the alkyl group include methyl, ethyl, butyl, isopropyl, t-butyl, hydroxyethyl, methoxyethyl, cyanoethyl, trifluoromethyl and the like.

The cycloalkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ includes a cycloalkyl group having a substituent and an unsubstituted cycloalkyl group. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group. The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms. Examples of the cycloalkyl group include cyclohexyl.
The aralkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ includes an aralkyl group having a substituent and an unsubstituted aralkyl group. Examples of the substituent include halogen atoms such as an alkyl group having 1 to 6 carbon atoms, such as a methyl group and an ethyl group, a chloro group, and a bromo group, and a plurality of these substituents may be substituted. . The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms. Examples of the aralkyl group include benzyl and 2-phenethyl.

The aryl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ includes an aryl group having a substituent and an unsubstituted aryl group. The aryl group is preferably an aryl group having 7 to 12 carbon atoms. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, and an alkylamino group. Examples of the aryl group include phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl and the like.

  Specific examples of the azo dye represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  In the organic nanoparticle dispersion composition of the present invention, only one type of azo dye represented by the general formula (1) may be used, or a plurality of types may be used in combination. Moreover, you may use together with things other than the azo dye represented by General formula (1). The organic pigment used in combination is not limited in terms of hue. For example, perylene, perinone, quinacridone, quinacridonequinone, anthraquinone, anthanthrone, benzimidazolone, disazo condensation, disazo, azo, indanthrone, phthalocyanine, tria Examples thereof include reel carbonium, dioxazine, aminoanthraquinone, diketopyrrolopyrrole, thioindigo, isoindoline, isoindolinone, pyranthrone or isoviolanthrone pigment, or a mixture thereof.

  More specifically, for example, C.I. I. Pigment red 190 (C.I. No. 71140), C.I. I. Pigment red 224 (C.I. No. 71127), C.I. I. Perylene pigments such as CI Pigment Violet 29 (C.I. No. 71129); I. Pigment orange 43 (C.I. No. 71105), or C.I. I. Perinone pigments such as CI Pigment Red 194 (C.I. No. 71100); I. Pigment violet 19 (C.I. No. 73900), C.I. I. Pigment violet 42, C.I. I. Pigment red 122 (C.I. No. 73915), C.I. I. Pigment red 192, C.I. I. Pigment red 202 (C.I. No. 73907), C.I. I. Pigment Red 207 (C.I. No. 73900, 73906) or C.I. I. Pigment Red 209 (C.I. No. 73905), a quinacridone pigment, C.I. I. Pigment red 206 (C.I. No. 73900/73920), C.I. I. Pigment orange 48 (C.I. No. 73900/73920), or C.I. I. Quinacridone quinone pigments such as CI Pigment Orange 49 (C.I. No. 73900/73920); I. Anthraquinone pigments such as CI Pigment Yellow 147 (C.I. No. 60645); I. Anthanthrone pigments such as CI Pigment Red 168 (C.I. No. 59300); I. Pigment brown 25 (C.I. No. 12510), C.I. I. Pigment violet 32 (C.I. No. 12517), C.I. I. Pigment yellow 180 (C.I. No. 21290), C.I. I. Pigment yellow 181 (C.I. No. 11777), C.I. I. Pigment orange 62 (C.I. No. 11775), or C.I. I. Benzimidazolone pigments such as CI Pigment Red 185 (C.I. No. 12516); I. Pigment yellow 93 (C.I. No. 20710), C.I. I. Pigment yellow 94 (C.I. No. 20038), C.I. I. Pigment yellow 95 (C.I. No. 20034), C.I. I. Pigment yellow 128 (C.I. No. 20037), C.I. I. Pigment yellow 166 (C.I. No. 20035), C.I. I. Pigment orange 34 (C.I. No. 21115), C.I. I. Pigment orange 13 (C.I. No. 21110), C.I. I. Pigment orange 31 (C.I. No. 20050), C.I. I. Pigment red 144 (C.I. No. 20735), C.I. I. Pigment red 166 (C.I. No. 20730), C.I. I. Pigment red 220 (C.I. No. 20055), C.I. I. Pigment red 221 (C.I. No. 20065), C.I. I. Pigment red 242 (C.I. No. 20067), C.I. I. Pigment red 248, C.I. I. Pigment red 262, or C.I. I. Disazo condensation pigments such as CI Pigment Brown 23 (C.I. No. 20060); I. Pigment yellow 13 (C.I. No. 21100), C.I. I. Pigment yellow 83 (C.I. No. 21108), or C.I. I. Disazo pigments such as CI Pigment Yellow 188 (C.I. No. 21094); I. Pigment red 187 (C.I. No. 12486), C.I. I. Pigment red 170 (C.I. No. 12475), C.I. I. Pigment yellow 74 (C.I. No. 11714), C.I. I. Pigment yellow 150 (C.I. No. 48545), C.I. I. Pigment red 48 (C.I. No. 15865), C.I. I. Pigment red 53 (C.I. No. 15585), C.I. I. Pigment orange 64 (C.I. No. 12760), or C.I. I. Azo pigments such as C.I. Pigment Red 247 (C.I. No. 15915), C.I. I. Indanthrone pigments such as CI Pigment Blue 60 (C.I. No. 69800); I. Pigment green 7 (C.I. No. 74260), C.I. I. Pigment Green 36 (C.I. No. 74265), Pigment Green 37 (C.I. No. 74255), Pigment Blue 16 (C.I. No. 74100), C.I. I. Phthalocyanine pigments such as CI Pigment Blue 75 (C.I. No. 74160: 2) or 15 (C.I. No. 74160); I. Pigment blue 56 (C.I. No. 42800), or C.I. I. Triarylcarbonium pigments such as CI Pigment Blue 61 (C.I. No. 42765: 1); I. Pigment violet 23 (C.I. No. 51319) or C.I. I. Dioxazine pigments such as CI Pigment Violet 37 (C.I. No. 51345); I. Aminoanthraquinone pigments such as CI Pigment Red 177 (C.I. No. 65300); I. Pigment red 254 (C.I. No. 56110), C.I. I. Pigment Red 255 (C.I. No. 561050), C.I. I. Pigment red 264, C.I. I. Pigment red 272 (C.I. No. 561150), C.I. I. Pigment orange 71, or C.I. I. Diketopyrrolopyrrole pigments such as C.I. Pigment Orange 73; I. Thioindigo pigments such as CI Pigment Red 88 (C.I. No. 7313), C.I. Pigment Yellow 139 (C.I. No. 56298), C.I. I. Pigment Orange 66 (C.I. No. 48210) and the like, isoindoline pigments such as C.I. I. Pigment yellow 109 (C.I. No. 56284), or C.I. Pigment Orange 61 (C.I. No. 11295) and the like, isoindolinone pigments such as C.I. I. Pigment Orange 40 (C.I. No. 59700), or C.I. I. Pyranthrone pigments such as CI Pigment Red 216 (C.I. No. 59710), or C.I. I. And isoviolanthrone pigments such as CI Pigment Violet 31 (60010).

  In the organic nanoparticle dispersion composition of the present invention, two or more kinds of organic pigments or solid solutions of organic pigments can be used in combination. Examples of organic dyes include azo dyes, cyanine dyes, merocyanine dyes, and coumarin dyes. Examples of the polymer compound that forms the solid solution include polydiacetylene and polyimide.

[Good solvent for forming organic nanoparticles]
Next, the preferable good solvent at the time of organic nanoparticle preparation is demonstrated.
The good solvent is not particularly limited as long as it can dissolve the azo dye represented by the general formula (1) and is compatible with or uniformly mixed with the poor solvent used in preparing the organic nanoparticles. Regarding the solubility of the azo dye represented by the general formula (1) in a good solvent, the solubility of the azo dye represented by the general formula (1) is preferably 0.2% by mass or more. More preferably, it is at least mass%. This solubility may be the solubility when dissolved in an acidic or alkaline manner. In addition, the compatibility or uniform mixing property between the good solvent and the poor solvent is preferably such that the solubility of the good solvent in the poor solvent is 30% by mass or more, and more preferably 50% by mass or more.

  Examples of good solvents include aqueous solvents (eg, water, hydrochloric acid, aqueous sodium hydroxide), alcohol solvents, amide solvents, ketone solvents, ether solvents, aromatic solvents, carbon disulfide, and aliphatic solvents. Solvents, nitrile solvents, sulfoxide solvents, halogen solvents, ester solvents, ionic liquids, mixed solvents thereof, and the like, aqueous solvents, alcohol solvents, ester solvents, sulfoxide solvents or amide solvents. Are preferred, aqueous solvents, sulfoxide solvents or amide solvents are more preferred, and sulfoxide solvents or amide solvents are particularly preferred.

Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of amide solvents 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. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether solvent include dimethyl ether, diethyl ether, tetrahydrofuran and the like. Examples of the aromatic solvent include benzene and toluene. Examples of the aliphatic solvent include hexane. Examples of the nitrile solvent include acetonitrile. Examples of the sulfoxide solvent include dimethyl sulfoxide, diethyl sulfoxide, hexamethylene sulfoxide, sulfolane and the like. Examples of the halogen solvent include dichloromethane, trichloroethylene, and the like. Examples of the ester solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

The concentration of the azo dye represented by the general formula (1) ranges from a saturated concentration of the azo dye represented by the general formula (1) represented by the general formula (1) to a good solvent or about 1/100 of this in the dissolution conditions. desirable.
There are no particular limitations on the preparation conditions of a solution in which the azo dye represented by the general formula (1) is dissolved (hereinafter also simply referred to as an organic material 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 preparing the organic nanoparticle dispersion composition of the present invention, the azo dye represented by the general formula (1) is preferably uniformly dissolved in a good solvent, and is preferably dissolved acidic or alkaline. In general, in the case of a pigment having an alkaline and dissociable group in the molecule, alkali is used, and when there is no alkaline and dissociable group and there are many nitrogen atoms in the molecule that are prone to add protons, acidity is used. For example, quinacridone, diketopyrrolopyrrole, and disazo condensation pigments are alkaline, and phthalocyanine pigments are acidic.

Bases used for alkaline dissolution are inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or barium hydroxide, or trialkylamine, diazabicycloundecene (DBU), An organic base such as a metal alkoxide is preferable, but an inorganic base is preferable.
The amount of the base used is an amount capable of uniformly dissolving the azo dye represented by the general formula (1), and is not particularly limited. In the case of an inorganic base, it is preferably represented by the general formula (1). It is 1.0-30 molar equivalent with respect to an azo pigment | dye, More preferably, it is 1.0-25 molar equivalent, More preferably, it is 1.0-20 molar equivalent. 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 further preferably 20 to 100 molar equivalents with respect to the azo dye represented by the general formula (1). Molar equivalent.

The acid used for the acidic dissolution is preferably an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid, or an organic acid such as acetic acid, trifluoroacetic acid, oxalic acid, methanesulfonic acid, or trifluoromethanesulfonic acid. It is an inorganic acid. Particularly preferred is sulfuric acid.
The amount of the acid used is an amount capable of uniformly dissolving the azo dye represented by the general formula (1), and is not particularly limited, but is often used in an excessive amount as compared with the base. Regardless of the inorganic acid or organic acid, it is preferably 3 to 500 molar equivalents, more preferably 10 to 500 molar equivalents, and even more preferably 30 to the azo dye represented by the general formula (1). ~ 200 molar equivalents.

[Poor solvent when forming organic nanoparticles]
Next, the preferable poor solvent at the time of organic nanoparticle preparation is demonstrated.
The poor solvent is not particularly limited as long as it does not dissolve the organic material to be used and is compatible with the good solvent used in the preparation of the organic nanoparticles or mixed uniformly. The solubility of the azo dye represented by the general formula (1) in the poor solvent is preferably 0.02% by mass or less, and more preferably 0.01% by mass or less. The preferred range of the compatibility or uniform mixing property between the poor solvent and the good solvent is as described above.
Examples of the poor solvent include aqueous solvents (for example, water, hydrochloric acid, aqueous sodium hydroxide), alcohol solvents, ketone solvents, ether solvents, aromatic solvents, carbon disulfide, aliphatic solvents, nitriles. Examples thereof include a system solvent, a halogen solvent, an ester solvent, an ionic liquid, a mixed solvent thereof, and the like, and an aqueous solvent, an alcohol solvent, or an ester solvent is preferable.

Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, 1-methoxy-2-propanol and the like. Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of the ether solvent include dimethyl ether, diethyl ether, tetrahydrofuran and the like. Examples of the aromatic solvent include benzene and toluene. Examples of the aliphatic solvent include hexane. Examples of the nitrile solvent include acetonitrile. Examples of the halogen solvent include dichloromethane, trichloroethylene, and the like. Examples of the ester solvent include ethyl acetate, ethyl lactate, 2- (1-methoxy) propyl acetate and the like. The ionic liquids, for example, 1-butyl-3-methylimidazolium and PF ₆ ^-, etc. and salts thereof.

[Alkali-soluble binder]
When producing the organic nanoparticle dispersion composition of the present invention, an alkali-soluble binder having an acidic group is added during the formation of the organic nanoparticles. An alkali-soluble binder having an acidic group can be added to the organic material solution and / or the poor solvent. Alternatively, it is also preferable to add an alkali-soluble binder solution having an acidic group in another system when forming organic nanoparticles. Examples of the alkali-soluble binder having an acidic group (hereinafter simply referred to as “binder”) used in the production of the organic nanoparticle dispersion composition of the present invention include polar groups such as carboxylic acid groups and carboxylate groups in the side chain. Polymers having groups are preferred. 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-59-53836. 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 A coalescence etc. can be mentioned. Moreover, the cellulose derivative which has a carboxylic acid group 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. Particularly preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid, and others. And multi-component copolymers with these monomers. These binder polymers having a polar group may be used alone or in the form of a composition used in combination with a normal film-forming polymer. 200 mass parts is common and 25-100 mass parts is preferable.

  When the alkali-soluble binder having an acidic group is a polymer compound, the number of acidic groups in the polymer compound is not particularly limited, but when the number of repeating units contained in one molecule is 100, the acidic group It is preferable that the repeating unit which has is 5-100, and it is more preferable that it is 10-100. In the case of an alkali-soluble binder having (1) a repeating unit derived from a compound having a carboxyl group and (2) a repeating unit derived from a compound having a carboxylic acid ester group, the polymerization ratio is as follows. The mole% of the repeating unit (1) is preferably 5 to 40, the mole% of the repeating unit (2) is preferably 40 to 90, and the repeating unit other than the repeating unit (1) or (2). Is preferably 25 or less. The alkali-soluble binder having an acidic group is preferably a polymer compound, the molecular weight is preferably 3000 to 1000000, more preferably 4000 to 200000, and particularly preferably 5000 to 80000.

[Dispersant when forming organic nanoparticles]
In the organic nanoparticle dispersion composition of the present invention, a dispersant can be added to the organic material solution and / or the poor solvent. Or it is also preferable to add a dispersing agent solution at the time of organic nanoparticle formation by another system. The dispersant (1) has a function of quickly adsorbing on the surface of the deposited pigment to form fine pigment particles and (2) preventing these particles from aggregating again.
As the dispersant, for example, anionic, cationic, amphoteric, nonionic or pigmentary low molecular or high molecular dispersants can be used. The molecular weight of the polymer dispersant can be used without limitation as long as it can be uniformly dissolved in a solution, but preferably has a molecular weight of 1,000 to 2,000,000, and 5,000 to 1,000,000. 000 is more preferable, 10,000 to 500,000 is more preferable, and 10,000 to 100,000 is particularly preferable. (In the present invention, unless otherwise specified, molecular weight means weight average molecular weight. A polymer compound is a polydisperse system and does not necessarily have the same molecular weight or particle weight. The values obtained are average molecular weight averaged in some form, the main three being: 1) number average molecular weight Mn, 2) weight average molecular weight Mw, 3) Z average molecular weight Mz Yes, the relationship of Mn <Mw <Mz is established. ) Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, polyacrylamide, vinyl alcohol-vinyl acetate copolymer, and polyvinyl alcohol-partial formalized product. , Polyvinyl alcohol-partially butyralized, vinyl pyrrolidone-vinyl acetate copolymer, polyethylene oxide / propylene oxide block copolymer, polyacrylate, polyvinyl sulfate, poly (4-vinylpyridine) salt, polyamide, polyallylamine salt , Condensed naphthalene sulfonate, cellulose derivatives, starch derivatives 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 is preferable. These polymers can be used singly or in combination of two or more. These dispersants can be used alone or in combination. The dispersant used for dispersing the pigment is described in detail on pages 29 to 46 of “Pigment dispersion stabilization and surface treatment technology / evaluation” (Chemical Information Association, issued in December 2001).

  Examples of anionic dispersants (anionic surfactants) include N-acyl-N-alkyl taurine salts, fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphorus Examples include acid ester salts, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl sulfate ester salts, 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 dispersants can be used alone or in combination of two or more.

Cationic dispersants (cationic surfactants) include quaternary ammonium salts, alkoxylated polyamines, aliphatic amine polyglycol ethers, aliphatic amines, diamines and polyamines derived from aliphatic amines and fatty alcohols, fatty acids And imidazolines derived from these and salts of these cationic substances. These cationic dispersants can be used alone or in combination of two or more.
The amphoteric dispersant is a dispersant having both an anion group part in the molecule of the anionic dispersant and a cationic group part in the molecule of the cationic dispersant.
Nonionic dispersants (nonionic surfactants) include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, Examples thereof include glycerin fatty acid esters. Of these, polyoxyethylene alkylaryl ether is preferable. These nonionic dispersants can be used alone or in combination of two or more.

The pigment-based dispersant is defined as a pigment-based dispersant derived from an organic pigment as a parent substance and produced by chemically modifying the parent structure. For example, sugar-containing pigment dispersants, piperidyl-containing pigment dispersants, naphthalene or perylene-derived pigment dispersants, pigment dispersants having a functional group linked to the pigment parent structure via a methylene group, and polymer-modified pigment parents. Examples include a structure, a pigment dispersant having a sulfonic acid group, a pigment dispersant having a sulfonamide group, a pigment dispersant having an ether group, or a pigment dispersant having a carboxylic acid group, a carboxylic ester group, or a carboxamide group. In addition, compounds represented by the general formula (I) described in JP-A-2000-239554 are also preferably used.
In order to further improve the uniform dispersibility and storage stability of the organic material, the content of the dispersant is preferably in the range of 0.1 to 1000 parts by mass, more preferably 100 parts by mass of the organic material. Is in the range of 1 to 500 parts by mass, more preferably in the range of 10 to 250 parts by mass. If the amount is less than 0.1 parts by mass, the dispersion stability of the organic pigment fine particles may not be improved.

[Mixing conditions when forming organic nanoparticles]
The mixing method of the organic material solution and the poor solvent is not particularly limited, but it is preferable to stir one and add the other to it, and it is particularly preferable to add the organic material solution to the stirred poor solvent. . 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. One addition port may be used for addition in the liquid, or a plurality of addition ports may be used. The addition diameter is preferably 20 mm or less, and more preferably 10 mm or less.
The stirring speed for stirring one is preferably 100 to 10000 rpm, more preferably 150 to 8000 rpm, and particularly preferably 200 to 6000 rpm.
The ratio of the organic material solution to the poor solvent (good solvent / poor solvent) is preferably 1/50 to 2/3 by volume, more preferably 1/40 to 1/2, and particularly preferably 1/20 to 3/8. .
The concentration of the dispersion after preparing the organic nanoparticles is not particularly limited as long as the organic nanoparticles can be dispersed, but it is preferably in the range of 10 to 40,000 mg of nanoparticles with respect to 1000 ml of the dispersion solvent, more preferably It is the range of 20-30000 mg, Most preferably, it is the range of 50-25000 mg.

[Particle size and monodispersity of organic nanoparticles]
Regarding the particle size of organic nanoparticles, there is a method of expressing the average size of the population by quantifying by a measurement method, but as a common method, the mode diameter indicating the maximum value of the distribution, the center of the integral distribution curve There are median diameters corresponding to the values, various average diameters (number average, length average, area average, weight average, volume average, etc.). In the present invention, unless otherwise specified, the particle diameter is the number average. The diameter. The particle size of the organic nanoparticles (primary particles) formed when producing the organic nanoparticle dispersion composition of the present invention is 1 μm or less (for example, crystals or aggregates of that size), and 1 to 200 nm. It is preferable that it is 2-100 nm, and it is especially preferable that it is 5-80 nm.
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. The monodispersity of the particles (primary particles) contained in the organic nanoparticle dispersion prepared when producing the pigment dispersion composition of the present invention, that is, Mv / Mn, is preferably 1.0 to 2.0. It is more preferably 1.0 to 1.8, and particularly preferably 1.0 to 1.5.

[Concentration of organic nanoparticle dispersion]
In the organic nanoparticle dispersion composition of the present invention, a mixed liquid (hereinafter also referred to as organic nanoparticle dispersion) obtained by mixing an organic material solution and a poor solvent to produce organic nanoparticles is concentrated and necessary. By desalting accordingly, it is possible to produce products suitable for color filter coating liquids and inkjet inks on an industrial scale.

Below, the method to concentrate an organic nanoparticle dispersion liquid is demonstrated.
The concentration method is not particularly limited as long as the organic nanoparticle dispersion liquid can be concentrated. For example, an extraction solvent is added to and mixed with the organic nanoparticle dispersion liquid, and the organic nanoparticles are concentrated and extracted into the extraction solvent phase. A method of filtering the extract with a filter to obtain a concentrated nanoparticle solution (concentration extraction method), a method of sedimenting and concentrating organic nanoparticles by centrifugation (centrifugation method), and desalination concentration by ultrafiltration A method (ultrafiltration method), a method of sublimating the solvent by vacuum freeze-drying, or drying and concentrating the solvent by heating or reduced pressure (drying method) is preferred. Or a combination thereof is very preferably used.
The concentration of the organic nanoparticles after concentration is preferably 1 to 100% by mass, more preferably 5 to 100% by mass, and particularly preferably 10 to 100% by mass.

(Concentrated extraction method)
The extraction solvent used in the concentrated extraction method is not particularly limited, but does not substantially mix with the dispersion solvent (for example, an aqueous solvent) of the organic nanoparticle dispersion (in the present invention, it does not substantially mix) It means that the solubility is low, and the amount of dissolution is preferably 50% by mass or less, more preferably 30% by mass or less), and it is preferably a solvent that forms an interface when allowed to stand after mixing. In addition, the extraction solvent should be a solvent that generates weak aggregation (which can be redispersed without applying high shearing force such as milling or high-speed stirring) in which the organic nanoparticles can be redispersed in the extraction solvent. preferable. In such a state, it is possible to easily remove the dispersion solvent such as water by filter filtration or the like while wetting the target organic nanoparticles with the extraction solvent without causing strong aggregation that changes the particle size. This is preferable. The extraction solvent is preferably an ester solvent, an alcohol solvent, an aromatic solvent or an aliphatic solvent, more preferably an ester solvent, an aromatic solvent or an aliphatic solvent, and particularly preferably an ester solvent.
Examples of the ester solvent include 2- (1-methoxy) propyl acetate, ethyl acetate, and ethyl lactate. Examples of the alcohol solvent include n-butanol and isobutanol. Examples of the aromatic solvent include benzene, toluene, xylene and the like. Examples of the aliphatic solvent include n-hexane and cyclohexane. Further, the extraction solvent may be a pure solvent based on the above preferred solvent or a mixed solvent composed of a plurality of solvents.

The amount of the extraction solvent is not particularly limited as long as the organic nanoparticles can be extracted, but is preferably smaller than the organic nanoparticle dispersion in consideration of concentration and extraction. When this is shown by volume ratio, when the organic nanoparticle dispersion liquid is 100, the extraction solvent to be added is preferably in the range of 1 to 100, more preferably in the range of 10 to 90, and 20 to 80. The range of is particularly preferable. If it is too much, it will take a lot of time for concentration, and if it is too little, extraction will be insufficient and nanoparticles will remain in the dispersion solvent.
After adding the extraction solvent, it is preferable to stir and mix so as to be in sufficient contact with the dispersion. A normal method can be used for stirring and mixing. Although there is no restriction | limiting in particular in the temperature when adding and mixing an extraction solvent, It is preferable that it is 1-100 degreeC, and it is more preferable that it is 5-60 degreeC. Any device may be used for adding and mixing the extraction solvent as long as each step can be preferably performed. For example, a separation funnel type device can be used.

(Ultrafiltration method)
In the case of ultrafiltration, for example, a method used for desalting / concentration of a silver halide emulsion can be applied. Research Disclosure No. 10208 (1972), No. 13 122 (1975) and No. 16 351 (1977) are known. The pressure difference and flow rate that are important as operating conditions can be selected with reference to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology Handbook”, Koshobo Publishing (1978), p275. It is preferable to find the optimum condition in order to suppress the aggregation of particles. In addition, there are two methods for replenishing a solvent that is lost due to membrane permeation: a constant volume method in which the solvent is continuously added and a batch method in which the solvent is intermittently added, but the desalting time is relatively short. The formula is preferred. As the solvent to be replenished, pure water obtained by ion exchange or distillation is used. However, a dispersant, a poor solvent for the dispersant may be mixed in pure water, or directly into the organic nanoparticle dispersion. It may be added.

(Centrifugation method)
The centrifuge used for concentration of the organic nanoparticles by centrifugation may be any device as long as it can precipitate the organic nanoparticles in the organic nanoparticle dispersion (or the organic nanoparticle concentrated extract). As a centrifuge, for example, in addition to a general-purpose device, a device with a skimming function (a function of sucking the supernatant layer during rotation and discharging it out of the system) or continuous centrifugation for continuously discharging solid matter Machine.
Centrifugation conditions are preferably 50 to 10000, 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, 0-60 degreeC is especially preferable.

(Drying method)
The apparatus used for concentration of the organic nanoparticles by drying under reduced pressure is not particularly limited as long as the solvent of the organic nanoparticle dispersion (or organic nanoparticle concentrated extract) can be evaporated. For example, a general-purpose vacuum dryer and a rotary pump, an apparatus that can be heated and reduced in pressure while stirring the liquid, and an apparatus that can be continuously dried by passing the liquid through a heated and reduced pressure tube.
The heating and drying temperature is preferably 30 to 230 ° C, more preferably 35 to 200 ° C, and particularly preferably 40 to 180 ° C. The pressure during decompression is preferably 100 to 100,000 Pa, more preferably 300 to 90,000 Pa, and particularly preferably 500 to 80,000 Pa.

  In the organic nanoparticle dispersion composition of the present invention, according to the concentration method as described above, the organic nanoparticles can be efficiently concentrated from the organic nanoparticle dispersion. Regarding the concentration ratio, for example, when the concentration of the nanoparticles in the organic nanoparticle dispersion as a raw material is 1, the concentration in the concentrated organic nanoparticle paste is preferably about 100 to 3000 times, more preferably about 500 to 2000 times. Can be concentrated.

[Redispersion of organic nanoparticle dispersion]
In the organic nanoparticle dispersion composition of the present invention, the concentrated organic nanoparticles are finely dispersed again in an organic solvent containing an alkali-soluble binder having an acidic group (in the present invention, the fine dispersion and Is to increase the degree of dispersion by deaggregating particles in the dispersion, and to finely redisperse after concentration is also called redispersion.)
For example, in color filter applications, it can be added to a vehicle and dispersed. The vehicle refers to a portion of a medium in which the pigment is dispersed when the paint is in a liquid state. The portion is a liquid that binds to an organic material and hardens the coating film (binder), and dissolves and dilutes the portion. Component (organic solvent). In the present invention, the binder used at the time of nanoparticle formation and the binder used for redispersion may be the same or different, and may be distinguished as a nanoparticle forming binder and a redispersed binder, respectively. .

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

In the above-described concentrated and extracted nanoparticle liquid, organic nanoparticles are usually agglomerated by concentration in a state that enables rapid filter filtration. In addition, organic nanoparticles concentrated by centrifugation or drying also aggregate due to concentration.
As a method of dispersing such aggregated nanoparticles (in the present invention, aggregated nanoparticles are those in which nanoparticles such as aggregates are gathered by secondary force), for example, a dispersion method using ultrasonic waves, 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 (refer to “Latest Pigment Dispersion Technology” Technical Information Association, 1995, p166). Therefore, the liquid temperature is preferably 1 to 100 ° C. -60 degreeC is more preferable. The temperature control method can be performed by controlling the temperature of the dispersion, controlling the temperature of the temperature adjusting layer that controls the temperature of the dispersion, or the like.

There are no particular restrictions on the disperser used to disperse the concentrated organic nanoparticles by applying physical energy, for example, kneader, roll mill, atrider, super mill, dissolver, homomixer, sand mill, etc. Machine.
It is also preferable to use again the compounds shown in [Dispersant for forming organic nanoparticles] as a dispersant used for forming organic nanoparticles during redispersion.

  In the organic nanoparticle dispersion composition of the present invention, re-dispersed organic nanoparticles (primary particles) can be made into finely dispersed particles, and the particle size can be preferably 1 to 200 nm. ˜100 nm is more preferred, and 5˜50 nm is particularly preferred. Further, the Mv / Mn of the re-dispersed particles is preferably 1.0 to 2.0, more preferably 1.0 to 1.8, and 1.0 to 1.5. Is particularly preferred.

The organic nanoparticles dispersed in the organic nanoparticle dispersion composition of the present invention and the colored photosensitive resin composition to be described later are intended despite the minute particle size of nanometer size (for example, 10 to 100 nm). Organic nanoparticles are concentrated and redispersed with particle size. For this reason, when used in a color filter, the optical density is high, the uniformity of the filter surface is excellent, the contrast is high, and the noise of the image can be reduced.
Furthermore, since the organic nanoparticles contained in the organic nanoparticle dispersion composition and colored photosensitive composition of the present invention are dispersed in a highly and uniformly finely divided state, the film thickness is small, A high color density is exhibited, and for example, a color filter or the like can be made thin.

Further, the organic nanoparticle dispersion composition and the colored photosensitive resin composition of the present invention contain a pigment exhibiting a clear color tone and high coloring power, for example, image formation for producing a color proof or a color filter. Useful as a material.
Furthermore, the organic nanoparticle dispersion composition and the colored photosensitive resin composition of the present invention can be used as an alkaline aqueous solution as a binder (binder) even for an alkaline developer used for exposure and development during the formation of a colored image. It uses a soluble material and can meet environmental requirements.

  Moreover, the organic nanoparticle dispersion composition of this invention and the organic solvent which has moderate drying property can be used as a solvent (dispersion medium of an organic material) used for a coloring photosensitive resin composition, and the point of drying after application | coating But it can satisfy that demand.

[Colored photosensitive resin composition]
The colored photosensitive resin composition used in the present invention (hereinafter also simply referred to as “the colored photosensitive resin composition of the present invention”) is at least (I) in the presence of an alkali-soluble binder (A) having an acidic group, A solution of an organic material dissolved in a good solvent and a poor solvent compatible with the solvent, and organic nanoparticles formed with the organic pigment as particles having a particle size of 1 μm or less; and (II) an alkali having an acidic group It contains a soluble binder (B), (III) monomer or oligomer, and (IV) a photopolymerization initiator or photopolymerization initiator system. However, (A) and (B) may be the same or different. The essential components (I) to (IV) in the colored photosensitive resin composition of the present invention will be described.

(1) Organic nanoparticles The method for producing organic nanoparticles has already been described in detail. The content of the organic nanoparticles is 3 to 60 mass with respect to the total solid content in the colored photosensitive resin composition (in the present invention, the total solid content refers to the total amount of the composition excluding the organic solvent). % Is preferable, and 5-40 mass% is 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, the coloring power is not sufficient. The organic nanoparticles functioning as a colorant preferably have a particle size of 0.1 μm or less, particularly 0.08 μm or less.

(2) Alkali-soluble binder The alkali-soluble binder (B) used for redispersion is not particularly limited as long as it has an acidic group, but those described in the above [Alkali-soluble binder] are preferably used. A compound having a structure similar to that of the alkali-soluble binder (A) at the time of forming the nanoparticles added during the formation of the organic pigment particles is preferable, and it is particularly preferable that the two are the same. The content of the redispersed alkali-soluble binder (the nanoparticle-forming alkali-soluble binder (A) may be the total content thereof when remaining) is based on the total solid content of the colored photosensitive resin composition 15-50 mass% is common and 20-45 mass% is preferable. If the amount is too large, the viscosity of the composition becomes too high, causing a problem in production suitability. If the amount is too small, there is a problem in forming a coating film.

(3) Monomer or oligomer The monomer or oligomer contained in the colored photosensitive resin composition of the present invention is a polymerizable component that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light. It is preferable. Examples of such monomers and oligomers 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, 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.

  These monomers or oligomers (monomers or oligomers having a molecular weight of 200 to 1000 are preferred) may be used alone or in admixture of two or more, and may be used for the total solid content of the colored photosensitive resin composition. The content is generally 5 to 50% by mass, and preferably 10 to 40% by mass. If the amount is too large, the viscosity of the composition becomes too high, causing a problem in production suitability. If the amount is too small, the curing power at the time of exposure is insufficient.

(4) Photopolymerization initiator or photopolymerization initiator system Photopolymerization initiator or photopolymerization initiator system contained in the colored photosensitive resin composition of the present invention (in the present invention, the photopolymerization initiator system is a plurality of compounds. And a vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660, which is described in US Pat. No. 2,448,828. An acyloin ether compound, an aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, A combination of a triarylimidazole dimer and a p-aminoketone described in US Pat. No. 3,549,367, JP-B 51-4 Benzothiazole compounds and trihalomethyl-s-triazine compounds described in US Pat. No. 516, trihalomethyl-triazine compounds described in US Pat. No. 4,239,850, trihalomethyl described in US Pat. No. 4,221,976 An oxadiazole compound etc. can be mentioned. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.

These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture 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 photopolymerization initiator system with respect to the total solid content of the colored photosensitive resin 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 it is too small, the exposure sensitivity will be too low.
As described above, the colored photosensitive resin composition of the present invention contains at least a monomer or oligomer that is a polymerizable component, and a photopolymerization initiator or photopolymerization initiator system. To give a colored photosensitive polymer film of the present invention.

(Other additives)
-Solvent-
In the colored photosensitive resin composition of the present invention, an organic solvent may be further used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like. As for content of a solvent, 10-95 mass% is preferable with respect to the resin composition whole quantity.

-Surfactant-
Conventionally used color filters have a problem that the color of each pixel becomes dark in order to achieve high color purity, and the film thickness unevenness of the pixel is recognized as color unevenness as it is. For this reason, it has been demanded to improve the film thickness variation during the formation (application) of the photosensitive resin layer that directly affects the film thickness of the pixel.
In the color filter of the present invention or the photosensitive resin transfer material of the present invention, the colored photosensitive resin can be controlled to have a uniform film thickness and effectively prevent coating unevenness (color unevenness due to film thickness fluctuation). It is preferable to include an appropriate surfactant in the composition.
Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600. The content of the surfactant is preferably 5% by mass or less with respect to the total amount of the resin composition.

-Thermal polymerization inhibitor-
The colored photosensitive resin composition of the present invention 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 based on the total amount of the resin composition.

-Supplementary dyes and pigments-
In the colored photosensitive resin composition of the present invention, a colorant (dye, pigment) can be added as necessary in addition to the organic material as long as the effects of the present invention are not impaired. In the case of using a pigment among the colorants, it is desirable that the pigment is uniformly dispersed in the colored photosensitive resin composition. Therefore, the particle diameter is preferably 0.1 μm or less, particularly 0.08 μm or less.
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 content of the auxiliary dye or pigment is preferably 5% by mass or less based on the total amount of the resin composition.

-UV absorber-
The colored photosensitive resin composition of the present invention may 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.
Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine) -Sebakei 4-t-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4-piperidenyl ) -Ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5-triazine- 2-yl] amino} -3-phenylcoumarin and the like. As for content of a ultraviolet absorber, 5 mass% or less is preferable with respect to the resin composition whole quantity.

  In addition, the colored photosensitive resin composition of the present invention may contain “adhesion aid” described in JP-A No. 11-133600, other additives and the like in addition to the above additives.

[Coating film of colored photosensitive resin composition]
The colored photosensitive resin composition of the present invention can be used as a coating film, and the composition components thereof are the same as those described in the above section [Colored photosensitive resin composition]. Moreover, although the thickness of the coating film of the colored photosensitive resin composition of this invention can be suitably determined with the use, it is preferable that it is 0.5-5.0 micrometers, and is 1.0-3.0 micrometers. More preferably.

(Slit nozzle)
In addition, although the said coating film can be formed by apply | coating and drying the coloring photosensitive resin composition of this invention by a normal application method, in this invention, it is a slit-like part in the part which discharges a liquid. It is preferable to apply by a slit-like nozzle having holes. 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.

[Photosensitive resin transfer material]
The azo dye of the present invention is a photosensitive resin transfer material (photosensitive resin transfer material having at least a photosensitive resin layer containing a colored photosensitive resin composition and described in JP-A-5-72724. That is, a film formed using an integrated film is preferable. As an example of the structure of the integral film, there is a structure in which a temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer / protective film are laminated in this order. The photosensitive resin transfer material containing the azo dye of the present invention (hereinafter also referred to as the photosensitive resin transfer material of the present invention) is obtained by forming a photosensitive resin using the above-described colored photosensitive resin composition of the present invention. preferable.

(Temporary support)
In the photosensitive resin transfer material of the present invention, the temporary support is flexible and does not cause significant deformation, shrinkage, or elongation even under pressure or under pressure and heating. Is preferred. Examples of such a temporary support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, a polycarbonate film, etc. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

(Thermoplastic resin layer)
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

(Middle layer)
In the photosensitive resin transfer material of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

(Protective film)
A thin protective film is preferably provided on the photosensitive resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the photosensitive resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material.

(Method for producing photosensitive resin transfer material)
The photosensitive resin transfer material of the present invention is obtained by, for example, applying a coating solution (a coating solution for a thermoplastic resin layer) in which an additive for a thermoplastic resin layer is dissolved on a temporary support and drying the thermoplastic resin layer. Then, apply and dry a solution of an intermediate layer material composed of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, and then apply and dry the photosensitive resin layer with a solvent that does not dissolve the intermediate layer. It can produce by providing.
In addition, a sheet provided with a thermoplastic resin layer and an intermediate layer on the temporary support and a sheet provided with a photosensitive resin layer on a protective film are prepared, and the intermediate layer and the photosensitive resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a photosensitive resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. It can also be produced by sticking them together so that the intermediate layer is in contact with it.

  In addition, although application | coating in the said preparation method can be performed with a normal coating apparatus etc., in this invention, the slit-shaped nozzle already demonstrated in the term of the coating film of a coloring photosensitive resin composition was used. It is preferable to use a coating apparatus (slit coater). Preferred specific examples of the slit coater are the same as described above.

(Film thickness of each layer)
In the photosensitive resin transfer material of the present invention, the thickness of the photosensitive resin layer is preferably 1.0 to 5.0 μm, more preferably 1.0 to 4.0 μm, and particularly preferably 1.0 to 3.0 μm. . Although not particularly limited, preferred film thicknesses of the other layers are 15 to 100 μm for the temporary support, 2 to 30 μm for the thermoplastic resin layer, 0.5 to 3.0 μm for the intermediate layer, and protection. The film is generally preferably 4 to 40 μm.

[Color filter and color filter manufacturing method]
(Photosensitive resin layer)
The color filter of the present invention can be 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. "See color TFT-LCD color filters, plants, Koseki, Fukunaga, Yamanaka" etc.).
The high contrast of the color filter means that 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.

  In the color filter of the present invention, the chromaticities of all single colors of red (R), green (G), and blue (B) by the F10 light source are the values shown in the table below (hereinafter referred to as “target” in the present invention). The difference (ΔE) with respect to chromaticity ”is preferably within 5 ranges, more preferably within 3 ranges, and particularly preferably within 2 ranges.

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.

The color filter of the present invention can be produced by a method such as a method in which a photosensitive resin layer is formed on a substrate, and exposure and development are repeated by the number of colors. If necessary, the boundary may be divided by a black matrix.
In the above production method, the method for forming the photosensitive resin layer on the substrate includes (a) a method of applying each of the colored photosensitive resin compositions with a normal coating apparatus or the like, and (b) the above-described method. Examples thereof include a method of using a photosensitive resin transfer material and affixing with a laminator.

(A) Application by coating apparatus When the color filter of the present invention is produced, a normal coating apparatus can be used for coating the colored photosensitive resin composition. The slit coater described in the section of [Coating Film] can be suitably used. Note that preferred specific examples of the slit coater are the same as described above. When the photosensitive resin layer is formed by coating, the film thickness is preferably 1.0 to 3.0 μm, more preferably 1.0 to 2.5 μm, and particularly preferably 1.0 to 2.0 μm.

(B) Pasting with a laminator When pasting with a laminator, the photosensitive resin transfer material of the present invention is used, and a film-like one having a photosensitive resin layer is heated and / or pressurized on a substrate described later or It can be affixed by pressure bonding or thermocompression bonding with a flat plate. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. In the case where the photosensitive resin layer is formed by the method described in the section [Photosensitive resin transfer material], the preferable thickness of the photosensitive resin layer is the (film thickness of each layer) of [photosensitive resin transfer material]. This is the same as the preferable thickness described in the section.

(substrate)
In the present invention, as the substrate on which the color filter is formed, for example, a transparent substrate is used, and a known glass plate such as a soda glass plate having a silicon oxide film on its surface, a low expansion glass, a non-alkali glass, a quartz glass plate, etc. Or a plastic film etc. can be mentioned.
Moreover, the said board | substrate can make favorable adhesion | attachment with a coloring photosensitive resin composition or the photosensitive resin transfer material by giving a coupling process previously. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. In addition, although it does not necessarily limit, as a film thickness of a board | substrate, 700-1200 micrometers is generally preferable.

(Oxygen barrier membrane)
In the color filter of the present invention, when the photosensitive resin layer is formed by application of a colored photosensitive resin composition, an oxygen-blocking film can be further provided on the photosensitive resin layer, thereby improving the exposure sensitivity. Can be up. Examples of the oxygen blocking film include those already described in the section of (Interlayer) of [Photosensitive resin transfer material]. Although not particularly limited, the thickness of the oxygen blocking film is generally preferably 0.5 to 3.0 μm.

(Exposure and development)
A predetermined mask is disposed above the photosensitive resin layer formed on the substrate, and then exposed from above the mask through the mask, the thermoplastic resin layer, and the intermediate layer, and then developed with a developer. By repeating this process for the number of colors, the color filter of the present invention can be obtained.
Here, the light source for the exposure can be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, etc. are mentioned. As an exposure amount, it is about 5-200 mJ / cm < ² > normally, Preferably it is about 10-100 mJ / cm < ² >.

  Moreover, there is no restriction | limiting in particular as said developing solution, Normal developing solutions, such as a thing of Unexamined-Japanese-Patent No. 5-72724, can be used. The developer is preferably one in which the photosensitive resin layer exhibits a dissolution type development behavior. For example, a developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of a miscible organic solvent may be added.

  Examples of organic solvents miscible with water include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like. The concentration of the organic solvent is preferably 0.1% by mass to 30% by mass.

Further, a normal surfactant can be further added to the developer. The concentration of the surfactant is preferably 0.01% by mass to 10% by mass.
As a development method, methods such as paddle development, shower development, shower & spin development, and dip development can be used.

Here, the shower development will be described. The uncured portion can be removed by spraying a developer onto the exposed photosensitive resin layer by shower. In addition, it is preferable to spray an alkaline solution having low solubility of the photosensitive resin layer by a shower or the like before development to remove the thermoplastic resin layer, the intermediate layer, and the like. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13.

In addition, when manufacturing the color filter of the present invention, as described in JP-A No. 11-248922 and Japanese Patent No. 3255107, a base is formed by overlapping colored photosensitive resin compositions that form a color filter, It is preferable from the viewpoint of cost reduction that a transparent electrode is formed thereon and a spacer is formed by further overlapping the divisional alignment protrusions.
When the colored photosensitive resin composition is sequentially applied and stacked, the film thickness becomes thin each time the coating is performed due to the leveling of the coating solution. For this reason, it is preferable to overlap the four colors of K (black), R, G, and B and further overlap the divisional alignment protrusions. On the other hand, in the case of using a transfer material having a thermoplastic resin layer, it is preferable that three or two colors be overlapped because the thickness is kept constant.
The size of the base is preferably 25 μm or more, and particularly preferably 30 μm or more, from the viewpoint of preventing deformation of the photosensitive resin layer when the transfer material is laminated and laminating and maintaining a certain thickness.

[Liquid Crystal Display]
Since the color filter of the present invention is excellent in contrast, a liquid crystal display device using the color filter is excellent in descriptive power such as black spots, and is used for a large-screen liquid crystal display device such as a notebook computer display or a TV monitor. It can be used suitably.

  The azo dye represented by the general formula (1) can be synthesized, for example, by subjecting a diazo component compound and a coupler component compound to a coupling reaction according to Examples described later.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

Example 1
[Synthesis of Dye 1-1]

2.86 g (13.5 mmol) of diazo component A-1 was dispersed in 12 ml of acetic acid and 18 ml of propionic acid, and 40% of ONHSO ₄ was further added while maintaining the liquid temperature at 0 ° C. After this solution was reacted at 0 ° C. for 2 hours, 2.4 g (13.5 mmol) of coupler component B-1 was dispersed in 300 ml of water and added to the solution cooled to an internal temperature of 5 ° C. with stirring. When the reaction was allowed to proceed for 1 hour, a yellow precipitate was obtained. The precipitate was isolated by filtration, washed with water, and the process of heating and purifying the crystals with 100 ml of methanol was repeated twice to obtain 2.5 g of dye 1-1. The yield was 35.7%. λmax = 463.2 nm (in DMSO), ε = 38000 (in DMSO).

Example 2
[Synthesis of Dye 2-1]

2.86 g (13.5 mmol) of diazo component A-1 was dispersed in 12 ml of acetic acid and 18 ml of propionic acid, and 40% of ONHSO ₄ was further added while maintaining the liquid temperature at 0 ° C. After reacting this solution at 0 ° C. for 2 hours, 4 g (13.5 mmol) of coupler component B-2 was dispersed in 300 ml of water and added to a solution cooled to an internal temperature of 5 ° C. with stirring, and a cup was added. When the ring reaction was carried out and the reaction was allowed to proceed for 1 hour, a yellow precipitate was obtained. The precipitate was isolated by filtration, washed with water, and the process of heating and purifying the crystals with 100 ml of methanol was repeated twice to obtain 2.0 g of dye 2-1. The yield was 33.5%. [lambda] max = 473.5 nm (in DMSO), [epsilon] = 39400 (in DMSO).

Example 3
[Synthesis of Dye 4-1]

2.86 g (13.5 mmol) of diazo component A-1 was dispersed in 12 ml of acetic acid and 18 ml of propionic acid, and 40% of ONHSO ₄ was further added while maintaining the liquid temperature at 0 ° C. After this solution was reacted at 0 ° C. for 2 hours, 2.0 g (13.5 mmol) of coupler component B-3 was dispersed in 300 ml of water and added to the solution cooled to an internal temperature of 5 ° C. with stirring. When the reaction was allowed to proceed for 1 hour, a yellow precipitate was obtained. The precipitate was isolated by filtration, washed with water, and the process of heating and purifying the crystals with 100 ml of methanol was repeated twice to obtain 1.8 g of dye 4-1. The yield was 37.1%. λmax = 451.5 nm (in DMSO), ε = 37000 (in DMSO).

Example 4
In addition, the dyes shown in the compound numbers of Table 2 below were synthesized in the same manner by the same method as in Synthesis Example 1 except that the types and amounts of the diazo component and the coupler component were changed. The yield and λmax (in DMSO) are also shown in Table 2 below.

Example 5
An organic material solution prepared by dissolving 6 g of compound (1-1) in a solution obtained by mixing dimethyl sulfoxide and 8 mol / l-potassium hydroxide aqueous solution 6: 1 so that the concentration of compound (1-1) is 150 mmol / L. A was prepared.
Separately, 7.5 g of a methacrylic acid / benzyl methacrylate copolymer (molar ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution), dispersant 6 g of polyvinylpyrrolidone ( Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000) was dissolved to prepare 50 ml of solution B using 1-methoxy-2-propyl acetate as the solvent.
Separately from these, water was prepared as a poor solvent.

Here, NP-KX- made by Nippon Seimitsu Chemical Co., Ltd. was added to 1000 ml of poor solvent water which was temperature controlled at 1 ° C. and stirred at 500 rpm by GK-0222-10 type Lamond Stirrer manufactured by Fujisawa Pharmaceutical Co., Ltd. Inject 200 ml at a flow rate of 50 ml / min using a 500 type large capacity non-pulsating flow pump, and at the same time, solution B is 100 ml at a flow rate of 25 ml / min using an NP-KX-500 type large capacity non-pulsating flow pump manufactured by Nippon Seimitsu Chemical Co., Ltd. By injecting, organic nanoparticles were formed to prepare an organic nanoparticle dispersion. When the particle size and monodispersity of this pigment dispersion were measured using Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., the number average particle size was 35 nm and Mv / Mn was 1.35.
To the prepared organic nanoparticle dispersion (nanoparticle concentration: about 0.5% by mass), 500 ml of 2- (1-methoxy) propyl acetate was added, and the mixture was stirred at 25 ° C. for 10 minutes at 500 rpm and allowed to stand for 1 day. The organic nanoparticles were extracted into a 2- (1-methoxy) propyl acetate phase to obtain a concentrated extract.

The concentrated extract obtained by extracting organic nanoparticles is filtered using a FP-010 type filter manufactured by Sumitomo Electric Fine Polymer Co., to obtain a paste-like concentrated organic nanoparticle liquid (nanoparticle concentration: 35% by mass). It was. A dispersion composition having the following composition was prepared using the paste.
18.3 g of the paste
Methacrylic acid / benzyl methacrylate copolymer * 15.8 g
1-methoxy-2-propyl acetate 45.3 g
* Mole ratio 28/72, weight average molecular weight: 30,000, 40% 1-methoxy-2-propyl acetate solution The dispersion composition having the above composition was zirconia having a diameter of 0.65 mm using a motor mill M-50 (manufactured by Eiger). Using beads, the mixture was dispersed at a peripheral speed of 9 m / s for 1 hour to obtain an organic nanoparticle dispersion composition A of the present invention. The number average particle diameter of the organic nanoparticles at this time was 37 nm, and Mv / Mn was 1.45.

Example 6
The organic nanoparticle dispersion composition B of the present invention was used in the same manner as in Example 5 except that the compounds (2-1), (3-1), and (4-1) were used in place of the compound (1-1). , C and D were prepared respectively.

Comparative Example 1
The following mixed liquid was dispersed with a motor mill M-50 (manufactured by Eiger) using zirconia beads having a diameter of 0.1 mm for 9 hours at a peripheral speed of 9 m / s to prepare a pigment composition E for comparison.
6.4 g of pigment (P.Y.150)
1-methoxy-2-propyl acetate 60.0g
Polyvinylpyrrolidone 6g
(Wako Pure Chemical Industries, Ltd., K30, molecular weight 40,000)

Example 7
The composition samples A to E obtained in Examples 5 and 6 and Comparative Example 1 were each applied on a glass substrate so as to have a thickness of 2 μm, thereby preparing samples. This sample was placed between two polarizing plates, and the amount of transmitted light was measured when the polarization axis was parallel and vertical, and the ratio was taken as the contrast (“1990 Seventh Color Optical Conference, 512-color display. 10.4 "size TFT-LCD color filter, planting, Koseki, Fukunaga, Yamanaka" etc.) Table 3 shows the results of contrast measurement of the samples obtained from the composition samples A to E.

As shown in Table 3, the dispersion compositions (composition samples A to D) of the present invention using the azo dye represented by the general formula (1) are comparative examples 1 prepared by an Eiger mill usually used in the industry. It was found that the contrast was excellent even when compared with the sample (composition sample E).

Claims (5)

An azo dye represented by the following general formula (1).

In General Formula (1), R ¹ represents a hydrogen atom, an alkyl group, or an aryl group, and A represents a heterocyclic group that forms a 5-membered or 6-membered ring. The azo dye according to claim 1, wherein A is a heterocyclic group represented by the following general formula (2), (3) or (4).

In the general formulas (2), (3), and (4), * represents a bonding site with an N atom, and R ² , R ³ , R ⁴ , and R ⁵ are each independently a hydrogen atom, a cyano group,- CONH _{2 represents} an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group.   A solution prepared by dissolving at least one azo dye represented by the general formula (1) according to claim 1 in a good solvent and a poor solvent compatible with the solvent in the presence of an alkali-soluble binder having an acidic group. An organic nanoparticle dispersion composition, wherein the mixture is mixed to form a mixed solution in which the dye is produced as organic nanoparticles having a particle size of 1 μm or less.   4. The organic nanoparticle composition according to claim 3, wherein the mixed solution is concentrated and / or desalted. (I) An alkali-soluble binder having an acidic group comprising a solution in which at least one azo dye represented by the general formula (1) according to claim 1 is dissolved in a good solvent and a poor solvent compatible with the solvent. (A) a mixed liquid prepared by mixing in the presence of (A) to produce the dye as organic nanoparticles having a particle size of 1 μm or less; (II) an alkali-soluble binder having an acidic group (B) [where (A) and (B) may be the same or different], and (III) a monomer or oligomer, and (IV) a photopolymerization initiator or a photopolymerization initiator system. And a colored photosensitive polymer obtained by polymerizing a polymerizable component in the composition.