JP2017058658A - Colored composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter excellent in fastness such as heat resistance, light fastness and chemical resistance, and high brightness and a high contrast ratio.SOLUTION: The colored composition for a color filter comprises a colorant, a specific naphthol azo pigment, a dispersant (X) having a polyester moiety X1' having a specific carboxyl group and a vinyl polymer moiety X2' having a thermally crosslinking functional group, a binder resin, and a solvent.SELECTED DRAWING: None

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, a high temperature treatment of generally 200 ° C. or higher, preferably 230 ° C. or higher is required in the production process for forming the color filter. Therefore, at present, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used for color filters.

  However, in general, a color filter in which a pigment is dispersed has a problem that the degree of polarization controlled by the liquid crystal is disturbed due to light scattering by the pigment. That is, since light leaks when light must be blocked (OFF state) or transmitted light attenuates when light must be transmitted (ON state), display devices in the ON state and the OFF state There is a problem that the upper luminance ratio (contrast ratio) is low.

  Therefore, in recent years, pigments contained in the filter segment are often used after being refined in order to realize high brightness and high contrast of the color filter. However, various pigments (similarly called crudes having a particle size of 10 to 100 μm produced by chemical reaction, which are made into a mixture of primary particles and aggregated secondary particles by pigmentation treatment) Even if the particles are refined by the refinement treatment method, the pigments whose primary particles or secondary particles have been refined generally tend to agglomerate. When the refinement is too advanced, a huge lump of pigment solid is formed. End up. Furthermore, even if the pigment that has been refined further is dispersed in a pigment carrier containing a resin or the like, and the secondary particles of the pigment are stabilized as close as possible to the primary particles, a stable coloring composition is obtained. It is very difficult.

  For this reason, for example, pigment compositions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and in the worst case gelation occurs during storage. It may wake up and become difficult to use. Therefore, dispersibility can be achieved by using a structure-controlled one having a block structure (Patent Document 1) or a comb structure (Patent Document 2) or a resin-type dispersant (Patent Document 3) such as a polyester dispersant having a specific structure. A coloring composition having excellent storage stability and a high contrast ratio has been studied. However, even if these resin-type dispersants are used, it is not sufficient to improve the resistance of pigments whose surface area is increasing due to the progress of finer pigments. The present situation is that it is not sufficient with respect to resistance such as heat resistance, light resistance, and solvent resistance, resulting in poor state and poor leveling.

  As a method for obtaining a color filter having a high contrast ratio in a red filter segment which is one of the three primary colors (red, green, blue; RGB) of a color filter substrate, C.I. I. Pigment Red 254, C.I. I. A technique for producing a colored composition by adding Pigment Red 177 is used. However, C.I. I. Pigment Red 177 itself has low luminance and coloring power, so it cannot be used at a high content rate. I. Pigment Red 254 and C.I. I. When Pigment Red 177 is contained, the luminance, coloring power, and contrast are lowered in terms of arithmetic average, and as long as the combination of these conventionally used red pigments and yellow pigments can be used, the high contrast ratio and the high brightness are the limits. This is the current situation.

  Therefore, in order to realize a high contrast ratio and high brightness in recent years, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. It has been proposed to use an azo pigment such as Pigment Orange 38 as the main pigment.

  However, naphtholazo pigments have an affinity for the solvent of the pigment itself, the acidity of the pigment surface, etc. I. Pigment red 254 and C.I. I. Since it is different from CI Pigment Red 177 and the like, it has the disadvantages of being inferior in dispersibility, fluidity and storage stability, and also inferior in heat resistance and solvent resistance, and a practical color filter has not been obtained.

JP 2002-31713 A Japanese Patent Laid-Open No. 11-1515 International Publication No. 2008/007776 Pamphlet

  Accordingly, an object of the present invention is to provide a coloring composition for a color filter which is excellent in fastness such as heat resistance, light resistance and chemical resistance and has a high luminance and contrast ratio.

  As a result of intensive studies to solve the above problems, the present inventors have found that a coloring composition containing a naphtholazo pigment [A1] represented by the general formula (1) and a dispersing agent (X) It has been found that the above problems can be solved by a product.

That is, the present invention is a color filter coloring composition containing a colorant, a dispersant (X), a binder resin, and a solvent,
The colorant contains a naphtholazo pigment [A1] represented by the following general formula (1), and the dispersant (X) is one or more selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2) A polyester portion (X1 ′) having a carboxyl group obtained by reacting an acid anhydride group in the acid anhydride (b) with a hydroxyl group in the hydroxyl group-containing compound (a);
The present invention relates to a red coloring composition for a color filter, characterized by having a vinyl polymer portion X2 ′ formed by radical polymerization of an ethylenically unsaturated monomer (c) and having a thermally crosslinkable functional group.

General formula (1)
[In General Formula (1), each A independently represents a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an _-SO 2 ^{NHR 12,} representative of at least one trifluoromethyl group among R 2 to R ^6. R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  In the present invention, the dispersant (X) is at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group. It is related with the coloring composition for the said color filter characterized by the above-mentioned.

  The present invention also relates to the color composition for color filters, wherein the solvent contains a solvent (W1) containing a hydroxyl group having a boiling point of 100 ° C. to 250 ° C.

  The present invention further relates to the red coloring composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  Furthermore, the present invention relates to a color filter comprising a red filter segment formed from the red coloring composition for a color filter on a substrate.

Hereinafter, the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” in this specification means a color index (CI).

<Colorant>
The colorant in the coloring composition for a color filter of the present invention is characterized by containing a naphtholazo pigment [A1] represented by the general formula (1).

General formula (1):
[In General Formula (1), each A independently represents a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an _-SO 2 ^{NHR 12,} representative of at least one trifluoromethyl group among R 2 to R ^6. R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In the general formula (1), in A, the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group A trivalent metal salt (for example, sodium salt, potassium salt, aluminum salt, etc.) etc. are mentioned. Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, etc. However, it is not limited to these.

  In A, the “substituent” of the heterocyclic group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, or trifluoro group. Monovalent to trivalent metal of an acidic group selected from methyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group Salt (for example, sodium salt, potassium salt, aluminum salt etc.) etc. are mentioned. “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent group derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2-pyridyl. Group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2-oxazolyl group Group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N -Carbazolyl group etc. are mentioned.

^As the halogen atom in R 1 to R ^6, fluorine, chlorine, bromine, and iodine.

In addition, the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹² may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

As the colorant of the present invention,
A is preferably independently a hydrogen atom, a methyl group, a benzimidazolone group, or an optionally substituted phenyl group,
R ¹ is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or —OR ⁷ .
R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms,
R ^{2 to} R ⁶ are each independently preferably a hydrogen atom, a halogen atom, or a trifluoromethyl group, and at least one of R ^{2 to} R ⁶ is a trifluoromethyl group.
From the viewpoint of lightness, it is preferable that A is a phenyl group which may have a substituent. Furthermore, from the viewpoint of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁷ , and more preferably R ¹ is a methyl group or a methoxy group.

In addition, it is preferable that at least one of R ^{2 to} R ⁶ is a trifluoromethyl group because miniaturization is easy.
Among these, R ⁵ is preferably a -trifluoromethyl group, and R ² is preferably a -Cl group. By satisfying these requirements, the pigment can be made finer, so that high contrast can be achieved.

  The colorant of the present invention may have a chemical structure of the general formula (1) or a tautomer thereof, and may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  Specific examples of the azo compound used in the colorant of the present invention include the azo compounds shown in Table 1 below, but the present invention is not limited thereto. In Table 1, Ph represents a phenyl group.

(Method for producing naphtholazo pigment [A1])
The naphthol azo pigment [A1] of the present invention can be produced by a coupling reaction of a diazonium salt and a β-naphthol, as is well known in the pigment field. Also, as described below, two or more naphthol azo pigments can be synthesized simultaneously by using aromatic amines (diazo component), β-naphthols (coupler component), or both in the reaction. A plurality of naphthol azo pigment species may be included. In this case, a pigment composition that is excellent in miniaturization and gives excellent lightness may be obtained, which is more preferable.

  By simultaneously synthesizing two or more naphthol azo pigments, crystal growth can be inhibited, fine pigment particles can be obtained, and lightness can be improved for reasons such as improved transparency.

  The naphtholazo pigment [A1] is prepared by first adding an amine (diazo component) represented by the following general formula (3) in an acidic aqueous solution to which hydrochloric acid, sulfuric acid, acetic acid or the like is added, nitrous acid, nitrite or A diazonium salt represented by the following general formula (4) obtained by diazotization with a nitrite is produced.

General formula (3)

General formula (4)

[In General Formulas (3) and (4), A and R ¹ have the same meanings as in General Formula (1). X ⁻ represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. preferably chloride, _bromide, CH 3 COO ^- and the like.

  Next, the diazonium salt represented by the general formula (4) and the β-naphthols (coupling component) represented by the following general formula (5) are usually reacted at 5 ° C. to 70 ° C. in an aqueous solvent. And post-treatment by a conventional method to produce a naphtholazo pigment [A1] of the general formula (1). Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the naphthol azo pigment [A1] of this invention is not limited to these methods.

General formula (5)

[R < ² > -R < ⁶ > is synonymous with the thing in General formula (1) in General formula (5). ]

Moreover, when manufacturing simultaneously 2 or more types of naphthol azo pigment seed | species, the method described below is mentioned, for example.
First, a mixture of at least one aromatic amine (diazo component) represented by the following general formula (3) is added to a nitrous acid, nitrite or nitrous acid in an acidic aqueous solution to which hydrochloric acid, sulfuric acid or acetic acid is added. A mixture of diazonium salts represented by the following general formula (4) obtained by diazotization with an ester is produced.

General formula (3)

General formula (4)

[In General Formulas (3) and (4), A and R ¹ have the same meanings as in General Formula (1). X ⁻ represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. preferably chloride, _bromide, CH 3 COO ^- and the like.

Subsequently, the diazonium salt represented by the general formula (4), the β-naphthols (coupling component) represented by the following general formula (5), and the β-naphthols represented by the following general formula (10) The mixture with (coupling component) is usually reacted in an aqueous solvent at 5 ° C. to 70 ° C. and subjected to a post-treatment by a conventional method to obtain a naphthol azo pigment [A1] of the general formula (1) and the general formula A pigment composition containing the naphtholazo pigment [A ′] represented by (6) can be produced. At this time, A ¹ in the general formula (6) is the same as A in the general formula (1), and R ⁵¹ is the same pigment as R ¹ .
Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the naphthol azo pigment [A1] of this invention is not limited to these methods.

General formula (5)

[R < ² > -R < ⁶ > is synonymous with the thing in General formula (1) in General formula (5). ]

General formula (10)

  The mixing weight ratio of the aromatic amines of the general formula (3) and the mixing weight ratio of the β-naphthols of the general formulas (5) and (10) used in the reaction is between 60:40 and 100: 0, respectively. Can be set. By adjusting the mixing weight ratio, a pigment composition having a target weight ratio can be obtained.

Thus, a coupler component composed of a mixture of a naphthol compound represented by the general formula (5) and a naphthol compound represented by the general formula (10), and a diazo compound of an aromatic amine represented by the general formula (3) To produce a colorant containing an azo pigment represented by the general formula (1) and the general formula (6).
Such a colorant is excellent in lightness and contrast ratio, and is preferable.
At this time, the mass ratio of the mixture of the naphthol compound represented by the general formula (5) and the naphthol compound represented by the general formula (10) is preferably 60:40 to 100: 0, In some cases, the naphthol azo pigment [A1] represented by the general formula (1) is the only product.

(Other colorants)
The color composition for color filter of the present invention includes other pigments or dyes other than the naphthol azo pigment [A1] of the above general formula (1) within the range of not impairing the effects of the present invention in order to adjust chromaticity. These colorants may be used in combination. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

Colorants that can be used in combination include pigments such as diketopyrrolopyrrole pigments, azo pigments other than the naphtholazo pigment [A1] of the general formula (1) such as azo, disazo, or polyazo, aminoanthraquinone, diamino Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindolinone pigment, isoindolinone pigment Examples thereof include pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.
Examples of the dye include xanthene dyes, azo (pyridone, barbituric acid, metal complex, etc.) dyes, disazo dyes, anthraquinone dyes, and methine dyes. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

  Among these, azo pigments other than the naphthol azo pigment [A1] of the general formula (1), diketopyrrolopyrrole pigments, and anthraquinone pigments are preferable from the viewpoint of brightness and coloring power.

  Examples of the azo pigment other than the naphthol azo pigment [A1] represented by the general formula (1) include the naphthol azo pigment [A ′] represented by the general formula (6), and other azo pigments [C]. The naphtholazo pigment [A ′] represented by the general formula (6) is preferable because of its high brightness and contrast ratio.

(Naphthol azo pigment [A '])
The naphthol azo pigment [A ′] is a naphthol azo pigment represented by the general formula (6).
General formula (6)

[In General Formula (6), A ¹ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ¹⁵⁷ or —COOR ¹⁵⁸ . R ¹⁵⁷ and R ¹⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In A ¹ , the “substituent” of the phenyl group which may have a substituent and the “substituent” of the heterocyclic group which may have a substituent are the “substituent” in A of the general formula (1). Is the same as the substituent.

In addition, the alkyl group having 1 to 4 carbon atoms in R ¹⁵¹ , R ¹⁵⁷ , and R ¹⁵⁸ may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Isobutyl group, sec-butyl group, and tert-butyl group.

As a pigment, from the viewpoint of lightness, A ¹ is preferably a phenyl group which may have a substituent. Furthermore, from the viewpoints of lightness and dispersibility, R ¹⁵¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ¹⁵⁷ , and more preferably R ¹⁵¹ is a methyl group or a methoxy group.

  The colorant of the present invention may have a chemical structure of the general formula (6) or a tautomer thereof, or may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  When the colorant contains a naphthol azo pigment [A ′] represented by the general formula (6), it is represented by the naphthol azo pigment [A1] represented by the general formula (1) and the general formula (6). The weight ratio of the naphtholazo pigment [A ′] is preferably in the range of 60.0: 40.0 to 95.0: 5.0. More preferably, it is the range of 70.0: 30.0-90.0: 10.0. When the content of the naphtholazo pigment [A] is 60 or more or 95 or less, it is preferable because more excellent brightness can be obtained.

  Examples of the naphthol azo pigment represented by the general formula (6) include C.I. I. And CI Pigment Red 176.

(Other azo pigments [C])
Other azo pigments [C] include naphthol azo pigments [A1] represented by the general formula (1), azos other than the azo pigments [A ′] represented by the general formula (6), disazo, or polyazo And pigments.
Examples of such pigments include C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 95, 112, 114, 119, 136, 144, 164, 166, 170, 171, 175, 185, 208, 213, 214, 220, 221, 242, 253, 256, 258, C.I. I. Pigment Orange 1, 4, 15, 16, 22, 24, 38, 74, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 49, 55, 60, 63, 65, 73, 74, 75, 77, 81, 83, 87, 97, 98, 105, 106, 111, 113, 114, 116, 124, 126, 127, 130, 152, 155, 165, 167, 170, 172, 174, 176, 205, 214, 219 or the like. Among these, from the viewpoint of hue, brightness, and contrast ratio, C.I. I. Pigment red 185, 242 and C.I. I. Pigment Orange 38 is desirable.

  Specific examples of red pigments that can be used in combination are C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Use red pigments such as 166, 168, 176, 177, 178, 179, 184, 185, 187, 200, 202, 210, 221, 242, 246, 254, 255, 264, 270, 272, and 279 together Can do. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment Red 242 is preferably used, and these may be used together.

Examples of orange pigments and yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, and 214, and the like.
Examples of the orange pigment include C.I. I. Pigment orange 38, 43, 71, or 73.
Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment yellow 138, 139, 150, C.I. I. Pigment Orange 38 is preferable.

Moreover, as a pigment | dye used together, the diketopyrrolopyrrole pigment represented by following General formula (2) is preferable.
General formula (2)
[In general formula (2),
B, C, D and E are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl. _{^{group, -CF 3, -OR 13, -SR}} 14, -N (R 15) R 16, -COOR 17, -CONH 2, -CONHR 18, -CON (R 19) R 20, -SO 2 NH 2, -SO ₂ NHR ^21, or _a ^{-SO 2 N (R 22) R} 23,
R ^{13 to} R ²³ are each independently an alkyl group having 1 to 12 carbon atoms, a phenyl group that may have a substituent, or an aralkyl group that may have a substituent. ]

  Specific examples of the diketopyrrolopyrrole pigment represented by the general formula (2) that can be used in the present invention are listed below, but are not limited thereto.

Among the diketopyrrolopyrrole pigments represented by the general formula (2) that can be used in the present invention, the formula (2-1), the formula (2-2), the formula (2-3), and the formula (2-4) ), Formula (2-19), and Formula (2-20) are preferable from the viewpoints of brightness, contrast, and crystal precipitation suppression effect. In particular, from the viewpoint of brightness, the formulas (2-19) and (2-20) are preferable. Further, R ^{18 to} R ²⁰ in the formulas (2-3) and (2-4) are an alkyl group having 4 or more carbon atoms, or a phenyl group which may have a substituent. From the point of view, it is preferable. The reason why these are effective in increasing contrast and suppressing crystal precipitation is because of the steric hindrance effect due to bulky substituents such as carboamide groups, phenyl groups, and t-butyl groups having an alkyl group having 4 or more carbon atoms. This is thought to be due to the suppression of aggregation. Moreover, the diketopyrrolopyrrole pigment having a carboamide group, a phenyl group, or a t-butyl group has excellent color characteristics.

The dyes that can be used in combination are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes.
Among these, use of a xanthene oil-soluble dye, a xanthene basic dye, and a xanthene acid dye is preferable because of excellent hue. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like. Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP
), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these dyes, C.I., which is a rhodamine acid dye, is particularly excellent in terms of color developability, heat resistance and light resistance. I. Most preferably, Acid Red 52 is used.

  When used in combination with the above-mentioned red pigment, yellow pigment, orange pigment, and dye, the content of the naphtholazo pigment [A1] described by the general formula (1) is 10 to 90 wt% in a total of 100 wt% of the colorant. %, Preferably 20 to 80% by weight. By being in this content range, the chromaticity region can be expanded.

(Miniaturization of colorant)
The colorant for color filter of the present invention is used for color filters by obtaining finer colorant particles by a salt milling process or the like as necessary in order to obtain high brightness and high contrast when used as a colored composition. It can be suitably used as a colorant. The primary particle diameter of the colorant is preferably 10 nm or more in order to improve dispersibility in the colorant carrier. Moreover, in order to obtain a filter segment with high contrast, the thickness is preferably 50 nm or less.

  Salt milling is a process of heating a mixture of a colorant, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the colorant is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of subjecting the colorant to salt milling, it is possible to obtain a colorant having a sharp particle size distribution in which the primary particle size is very fine and the width of the distribution is widened.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight based on the total weight of the pigment (100% by weight) from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the colorant and water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the colorant (100% by weight).

  When salt milling the colorant, a resin may be added as necessary. Here, the type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by weight based on the total weight of the colorant (100% by weight).

<Dispersant>
The dispersant (X) of the present invention is composed of two sites X1 ′ and X2 ′, and it is impossible to specify and describe how these sites are bound. Since it is not realistic, it is described by the manufacturing method.
In general, a dispersant has a structure of a site that adsorbs to a colorant and a site that has a high affinity for a colorant carrier and a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance between these two sites. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the colorant and the affinity to the colorant carrier and the solvent as the dispersion medium are very important. The colorant carrier referred to here comprises a resin and its precursor or a mixture thereof obtained by removing the colorant component and the dispersant from the solid content.
The dispersant of the present invention is characterized by containing a dispersant (X).

<< Dispersant (X) >>
The dispersant (X) is an acid anhydride group in one or more acid anhydrides (b) selected from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2) and a hydroxyl group-containing compound (a). A polyester portion X1 ′ having a carboxyl group obtained by reacting with a hydroxyl group;
A vinyl polymer portion X2 ′ obtained by radical polymerization of an ethylenically unsaturated monomer (c) and having a thermally crosslinkable functional group;
The heat-crosslinkable functional group is a dispersant that is at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group. Moreover, when a crosslinkable functional group is a hydroxyl group, an oxetane group, a blocked isocyanate group, or a (meth) acryloyl group, it is preferable because it becomes excellent in solvent resistance.

  Here, the polyester portion X1 ′ of the main chain acts as a colorant adsorbing group and the vinyl polymer portion X2 ′ of the side chain acts as a colorant carrier affinity group, thereby suppressing aggregation of the colorant and improving stability. An excellent dispersion can be obtained. In addition, since the vinyl polymer portion X2 ′ in the side chain in the dispersant (X) has a thermally crosslinkable group, the coloring composition contained together with the dispersant (X) and the epoxy compound is cured. Excellent chemical and solvent resistance.

  The content of the dispersant (X) is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 60 parts by weight, and still more preferably 5 to 40 parts by weight with respect to 100 parts by weight of the colorant. When content of dispersing agent (X) exists in this range, it can be excellent in dispersibility and tolerance.

Further, the weight average molecular weight of the dispersant (X) is preferably 2,000 to 100,000.
If the weight average molecular weight is less than 2,000, the stability of the pigment composition may decrease, and if it exceeds 100,000, the interaction between the resins may become strong and the coloring composition may increase in viscosity. . Further, the acid value of the obtained dispersant is preferably 5 to 200 mgKOH / g. More preferably, it is 5-150 mgKOH / g, Most preferably, it is 5-100 mgKOH / g. If the acid value is less than 5 mgKOH / g, the ability to adsorb to the colorant may be reduced, resulting in a problem in dispersibility. If the acid value exceeds 200 mgKOH / g, the interaction between the resins becomes strong and the viscosity of the colored composition is high. There is a case.

Subsequently, each component of the dispersant (X) will be described.
[Hydroxyl-containing compound (a)]
The hydroxyl group-containing compound is not particularly limited as long as it has a hydroxyl group in the molecule, but is preferably a polyol having two or more hydroxyl groups in the molecule, and in particular, two hydroxyl groups and one in the molecule. It is preferable that it is a compound (a1) which has a thiol group.

[Compound having two hydroxyl groups and one thiol group in the molecule (a1)]
Examples of the compound (a1) having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1, 2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, Examples include 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[Other polyols (a2)]
As other polyols (a2) that can be used, there are those belonging to the following groups (1) to (7) as long as only typical ones are exemplified. By using these polyol compounds in combination, it becomes easy to adjust the density of the carboxylic acid group and the ratio of the solvent dissolving portion.

  (1) ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, glycerin, or Polyhydric alcohols such as hexanetriol;

  (2) Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol Kind;

  (3) Various polyhydric alcohols as described above, and (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether; Modified polyether polyols obtained by ring-opening polymerization of

  (4) Polyester polyols obtained by co-condensation with one or more of the various polyhydric alcohols described above and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1 , 2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, etc. Resulting polyols;

  (5) Lactone obtained by polycondensation reaction of one or more of the various polyhydric alcohols described above with various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Lactone-based polyester polyols, or lactone-modified polyester polyols obtained by polycondensation reaction of various polyhydric alcohols, polycarboxylic acids, and various lactones;

  (6) Epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids, Epoxy-modified polyester polyols obtained by combining one or more of the polyester polyols during synthesis; or

  (7) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound, or hydroxyl group-containing silicon resin And other polymer polyols.

  The other polyol (a2) optionally added shown in (1) to (7) may be used alone or in combination of two or more, but the weight average molecular weight is From the viewpoint of solubility and dispersion stability, it is preferably 40 to 10,000, more preferably 100 to 2,000, and still more preferably 100 to 1,000. When the weight average molecular weight is less than 40, the effect of improving the compatibility and dispersion stability is small, and when the weight average molecular weight is 10,000 or more, the compatibility may be deteriorated.

  The number of hydroxyl groups in one molecule of the other polyol (a2) is not particularly limited as long as the intended dispersant can be synthesized, but a diol is preferable. In particular, by reacting with tetracarboxylic dianhydride (b1), carboxyl groups serving as pigment adsorbing groups can be regularly arranged in the main chain, which is advantageous for pigment dispersion. When many polyols having more than two hydroxyl groups are used, the main chain of the polyester may be branched and complicated and bulky, and it may be difficult to obtain a dispersion effect. For the purpose of adjusting the molecular weight of the polyester (X) and adjusting the viscosity of the dispersion, it should be minimized from the viewpoint of design.

[Acid anhydride (b)]
The acid anhydride (b) of the present invention contains one or more selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2).
The two anhydride groups of the tetracarboxylic dianhydride (b1) react with the hydroxyl groups of the hydroxyl group-containing compound (a), whereby the carboxyl groups that form the pigment adsorption groups are regularly formed on the main chain of the dispersant (X). This is advantageous for pigment dispersion.
When tricarboxylic anhydride (b2) is used, it can react with a hydroxyl group to form an ester bond, leaving a carboxyl group.

  In addition, polycarboxylic acid anhydrides other than tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2), dicarboxylic acid anhydrides, and anhydrides of compounds having 5 or more carboxylic acids can be used in combination. .

[Tetracarboxylic acid anhydride (b1)]
As tetracarboxylic dianhydride (b1) used in the present invention,
1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2.2.2] -Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and other aliphatic tetracarboxylic dianhydrides, pyromellitic dianhydride, ethylene glycol Dimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4 4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3 ', 4 , 4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilane tetracarboxylic dianhydride Anhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4, 4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- 4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxy) Enoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4 -Aromatic tetracarboxylic dianhydrides such as tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

  The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Since tetracarboxylic dianhydride forms a dispersant having two carboxyl groups in one unit of polyester by reaction with a polyol, the constitution of the dispersant (X) of the present invention from the viewpoint of pigment adsorptivity. Preferred as an element.

  Furthermore, what is preferably used in the present invention is an aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to a colorant, and more preferably a tetracarboxylic dianhydride having two or more aromatic rings. It is a thing. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids, and carboxylic acids having two or more aromatic rings are skeletons suitable for pigment adsorption and have high heat resistance.

  Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (11) or general formula (12).

General formula (11):
[In General Formula (11), k is 1 or 2. ]

Formula (12):

[In General Formula (12), Q ₁ represents a direct bond, —O—, —CO—, —COOCH ₂ CH ₂ OCO
_{-, - SO 2 -, -} C (CF 3) 2 -, the formula (13):

Or a group represented by the general formula (14):

It is group represented by these. ]

[Tricarboxylic anhydride (a2)]
Examples of the tricarboxylic acid anhydride (b2) include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydride and the like. Of these, aromatic tricarboxylic acid anhydrides are preferably used in the present invention from the viewpoint of adsorptivity to pigments.

The ratio of the acid anhydride group in one or more acid anhydrides (b) selected from the tetracarboxylic acid anhydride (b1) and the tricarboxylic acid anhydride (b2) to the hydroxyl group in the hydroxyl group-containing compound (a) The anhydride group / hydroxyl group is preferably 0.5 to 1.5.
When it is smaller than 0.5 or larger than 1.5, there are many portions that do not react with each other, and the intended dispersant is often not obtained.

[Ethylenically unsaturated monomer (c)]
The dispersant (X) of the present invention has a vinyl polymer site X2 ′ formed by radical polymerization of the ethylenically unsaturated monomer (c).
[Ethylenically unsaturated monomer (c1)]
The ethylenically unsaturated monomer (c1) is an ethylenically unsaturated monomer having a thermally crosslinkable group or an ethylenically unsaturated monomer for introducing a thermally crosslinkable group.
Such an ethylenically unsaturated monomer having a hydroxyl group (c1-1), an ethylenically unsaturated monomer having an oxetane group (c1-2), an ethylenically unsaturated monomer having a t-butyl group ( c1-3) and an ethylenically unsaturated monomer (c1-4) having a blocked isocyanate group are copolymerized to give a vinyl polymer portion X2 ′ heat crosslinkability. Groups can be introduced.
Or a hydroxyl group in a hydroxyl group-containing polymer obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing an ethylenically unsaturated monomer having a hydroxyl group (c1-1),
By reacting the isocyanate group in the ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group (c1-5), the (meth) acryloyl group is introduced into the vinyl polymer portion X2 ′. be able to.

  Moreover, content of such an ethylenically unsaturated monomer (c1) shall be 5-70 weight% on the basis (100 weight%) of the sum total of all the ethylenically unsaturated monomers (c). Is more preferable, and more preferably 10 to 50% by weight. When the content is 5% by weight or more, the cross-linking property is excellent and the resistance is better. When the content is less than 70% by weight, the stability is excellent.

(Ethylenically unsaturated monomer having a hydroxyl group (c1-1))
As the ethylenically unsaturated monomer (c1-1) having a hydroxyl group, any monomer having a hydroxyl group and having an ethylenically unsaturated double bond may be used. Is a (meth) acrylate monomer having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) ) Hydroxyalkyl (meth) acrylates such as acrylate and cyclohexanedimethanol mono (meth) acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide monomers having hydroxyl groups For example, N- (2-hydroxyethyl) (meth) acrylami N- (2-hydroxypropyl) (meth) acrylamide, N- (hydroxyalkyl) (meth) acrylamide such as N- (2-hydroxybutyl) (meth) acrylamide, or vinyl ether monomer having a hydroxyl group, For example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether, or an allyl ether monomer having a hydroxyl group, for example, , 2-hydroxyethyl allyl ether, 2- (or 3-) hydroxypropyl allyl ether, and hydroxyalkyl allyl ethers such as 2- (or 3- or 4-) hydroxybutyl allyl ether.

Also obtained by adding alkylene oxide and / or lactone to the above hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkylallyl ether. The ethylenically unsaturated monomer obtained can also be used as an ethylenically unsaturated monomer having a hydroxyl group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. What added both alkylene oxide and lactone may be used.

(Ethylenically unsaturated monomer having oxetane group (c1-2))
Examples of the ethylenically unsaturated monomer (c1-2) having an oxetane group include methacrylic acid (3-ethyloxetane-3-yl) methyl.
Examples of commercially available products include ETERNACOLL OXMA (methacrylic acid (3-ethyloxetane-3-yl) methyl) (manufactured by Ube Industries).

(Ethylenically unsaturated monomer having t-butyl group (c1-3))
Examples of the ethylenically unsaturated monomer (c1-3) having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

(Ethylenically unsaturated monomer having a blocked isocyanate group (c1-4))
Examples of the ethylenically unsaturated monomer (c1-4) having a blocked isocyanate group include 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate and 2-[(3,5-dimethyl). And pyrazolyl) carbonylamino] ethyl methacrylate.
Examples of commercially available products include Karenz MOI-BM (2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI-BP (2-[(3, 5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate) (made by Showa Denko) and the like.

(Has isocyanate group and (meth) acryloyl group
Ethylenically unsaturated monomer (c1-5))
The ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group is a compound having one isocyanate group and one or more (meth) acryloyl groups, and one isocyanate group , And a compound having one or two (meth) acryloyl groups are preferred. Specifically, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, or 1,1-bis (acryloyloxymethyl) ethyl isocyanate is preferable.
The ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group used in the present invention is not limited to the compounds exemplified above, but an isocyanate group and one or more (meth) acryloyl groups. As long as it has a group, it may have any structure. These may be used alone or in combination.

[Other ethylenically unsaturated monomers]
Other ethylenically unsaturated monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl, in addition to the above ethylenically unsaturated monomer (c1). (Meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) Alkyl (meth) acrylates such as acrylate and isobornyl (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
N-substituted type (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile. Here, (meth) acrylate refers to methacrylate or acrylate, and (meth) acrylamide refers to methacrylamide or acrylamide.

  Examples of monomers that can be used in combination with the acrylic monomer include styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and acetic acid. And fatty acid vinyls such as vinyl and vinyl propionate.

[Synthesis Method of Dispersant (X)]
Examples of the synthesis method of the dispersant (X) include, but are not limited to, the following synthesis methods (1) to (3).

[Synthesis Method (1)]
In the presence of the hydroxyl group-containing compound (a),
An ethylenically unsaturated monomer having an oxetane group (c1-2), an ethylenically unsaturated monomer having a t-butyl group (c1-3), and an ethylenically unsaturated monomer having a blocked isocyanate group ( a hydroxyl group in a vinyl polymer having two hydroxyl groups in one terminal region obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing at least one selected from the group consisting of c1-4);
By reacting with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2), an oxetane group, t A dispersant having a butyl group or a blocked isocyanate group is obtained.

  When the ethylenically unsaturated monomer (c1-1) having a hydroxyl group is used in such synthesis method 1, the acid anhydride group in the acid anhydride (b) is converted into an ethylenically unsaturated monomer (c1- Since it also reacts with the hydroxyl group of 1), the purpose of reacting with the hydroxyl group at one end of the vinyl polymer cannot be achieved, and the desired structure may not be obtained.

  At this time, an ethylenically unsaturated monomer (c1-2) having an oxetane group, an ethylenically unsaturated monomer (c1-3) having a t-butyl group, and an ethylenically unsaturated monomer having a blocked isocyanate group The content of the monomer (c1-4) is preferably 5 to 90% by weight, particularly preferably 20 to 60% by weight, based on the entire ethylenically unsaturated monomer (c). If it is 5% by weight or more, it becomes possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 90% by weight or less, it is preferable because the stability of the composition is good.

[Synthesis method (2)]
A hydroxyl group in the hydroxyl group-containing compound (a) is reacted with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2). In the presence of the compound produced by
Ethylenically unsaturated monomer having a hydroxyl group (c1-1), ethylenically unsaturated monomer having an oxetane group (c1-2), ethylenically unsaturated monomer having a t-butyl group (c1-3) ) And an ethylenically unsaturated monomer (c) containing at least one selected from the group consisting of an ethylenically unsaturated monomer (c1-4) having a blocked isocyanate group, thereby being crosslinkable. A dispersant having a hydroxyl group, an oxetane group, a t-butyl group, or a blocked isocyanate group as a group is obtained.

  At this time, an ethylenically unsaturated monomer having a hydroxyl group (c1-1), an ethylenically unsaturated monomer having an oxetane group (c1-2), an ethylenically unsaturated monomer having a t-butyl group ( The content of the ethylenically unsaturated monomer (c1-4) having c1-3) and the blocked isocyanate group is 5 to 90% by weight in the whole ethylenically unsaturated monomer (c). It is preferable to use 20 to 60% by weight. If it is 5% by weight or more, it becomes possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 90% by weight or less, it is preferable because the stability of the composition is good.

[Synthesis Method (3)]
A hydroxyl group in the hydroxyl group-containing compound (a) is reacted with an acid anhydride group in one or more acid anhydrides (b) selected from tetracarboxylic anhydride (b1) and tricarboxylic anhydride (b2). In the presence of the compound produced by
A hydroxyl group in a hydroxyl group-containing compound obtained by radical polymerization of an ethylenically unsaturated monomer (c) containing a hydroxyl group-containing ethylenically unsaturated monomer (c1-1);
A dispersant having a (meth) acryloyl group as a crosslinkable group is obtained by reacting one isocyanate group with an isocyanate group in the compound (c1-5) having one or more (meth) acryloyl groups. .

  The content of the ethylenically unsaturated monomer (c1-1) having a hydroxyl group is preferably 5 to 70% by weight, preferably 10 to 50% by weight, based on the entire ethylenically unsaturated monomer (c). It is particularly preferable to do this. If it is 5% by weight or more, it becomes possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 70% by weight or less, it is preferable because the stability of the composition is good.

At this time, the molar ratio of the hydroxyl group in the copolymer after radical polymerization to the isocyanate group in the ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group is determined after radical polymerization. The isocyanate group in the ethylenically unsaturated monomer (c1-5) having an isocyanate group and a (meth) acryloyl group is 0.2 to 1.0 mol with respect to 1 mol of the hydroxyl group in the hydroxyl group in the copolymer. The amount is preferably 0.3, more preferably 0.3 to 1.0 mol, and most preferably 0.5 to 1.0 mol. If the amount is less than 0.2 mol, the amount of (meth) acryloyl groups may be reduced, so that the curability may be insufficient. If the amount exceeds 1.0 mol, unreacted isocyanate groups are present in the resin. It may remain and storage stability may deteriorate.
The reaction temperature is 50 ° C to 150 ° C, preferably 70 ° C to 120 ° C. If the reaction temperature is less than 50 ° C, the reaction rate is slow, and if it exceeds 150 ° C, the urethane group produced by the reaction may be decomposed.

[Synthesis of polyester part X1 ']
The synthesis of the polyester portion X1 ′ is carried out in the acid anhydride group and the hydroxyl group-containing compound (a) in one or more acid anhydrides (b) selected from tetracarboxylic acid anhydride (b1) and tricarboxylic acid anhydride (b2). This is a step of reacting with the hydroxyl group.

(Reaction catalyst)
As the catalyst used for the production of the polyester portion X1 ′ of the present invention, a known catalyst can be used. As a catalyst, for example,
Triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, or 1,5-diazabicyclo- [4.3.0] A tertiary amine compound such as -5-nonene, or mono-n-butyltin (IV) oxide may be used.

(Reaction solvent)
In the production of the polyester part X1 ′ of the present invention, it is possible to produce only with the raw materials listed so far, but a solvent is used in order to avoid problems such as high viscosity and non-uniform reaction. Is preferred. There is no limitation in particular as a solvent used, A well-known thing can be used. Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, toluene, xylene, or acetonitrile. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

(Reaction temperature)
The reaction temperature for the synthesis of the polyester portion X1 ′ is 50 ° C. to 180 ° C., preferably 80 ° C. to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but the reaction may be stopped when 97% or more of the acid anhydride is half-esterified by acid value measurement.

[Synthesis of vinyl polymer portion X2 ']
In the dispersant (X), the vinyl polymer portion X2 ′ is obtained by radical polymerization of the ethylenically unsaturated monomer (c), and has a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and (meta ) It has at least one thermally crosslinkable functional group selected from the group consisting of acryloyl groups. Since this vinyl polymer portion X2 'functions as an affinity site for the solvent and colorant carrier as the side chain of the dispersant (X), it is stable even when fine pigments or dyes are used. It can be made excellent in properties. Moreover, by having a thermally crosslinkable group, the effect of improving the resistance of the epoxy resin and the coating film can be exhibited.

  The weight average molecular weight of the vinyl polymer portion X2 'is preferably 1000 to 20000, more preferably 2000 to 15000, still more preferably 2000 to 12000, and particularly preferably 3000 to 8000. This portion X2 'becomes an affinity portion for the solvent as the dispersion medium. If the weight average molecular weight of the vinyl polymer portion X2 'is less than 1000, the effect of steric repulsion by the solvent affinity portion is reduced, and it is difficult to prevent pigment aggregation and dispersion stability may be insufficient. On the other hand, if it exceeds 20000, the absolute amount of the solvent affinity part increases, and the dispersibility effect itself may be lowered. Further, the viscosity of the dispersion may increase.

The content of the ethylenically unsaturated monomer (c) is preferably 3 to 100 parts by weight with respect to 1 part by weight of the hydroxyl group-containing compound (a), and bulk polymerization or solution polymerization is preferably performed. More preferably, it is 8-25 weight part, More preferably, it is 10-20 weight part. If it exceeds 100 parts by weight, the molecular weight of the vinyl polymer site X2 ′ is too high, and the absolute amount increases as an affinity site for the pigment carrier and the solvent, and the dispersibility effect itself may decrease, When the weight is less than 10 weight, the molecular weight of the vinyl polymer portion X2 ′ is too low, and the effect of steric repulsion is lost as an affinity portion for the pigment carrier and the solvent, and it is difficult to suppress the aggregation of the pigment. There is.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer. As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxynedecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

In the case of solution polymerization, as a polymerization solvent, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, etc. are used, but are not particularly limited thereto. It is not a thing. These polymerization solvents may be used as a mixture of two or more.

  As the dispersant (X), known techniques described in International Publication No. 2008/007776 pamphlet, JP 2009-155406 A, JP 2011-157416 A, and the like can be used.

《Other dispersants》
The coloring composition for a color filter of the present invention may be used in combination with other dispersants.
Specific examples of other dispersants include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified polymer Acrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, it can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Binder resin>
The binder resin disperses, dyes, or penetrates the colorant, and examples thereof include a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

<Solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1, 4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m Xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, , N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p -Diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate , Ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene Glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl Ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propio Over DOO, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  From the viewpoint of viscosity characteristics and contrast ratio, the solvent (W1) containing a hydroxyl group having a boiling point of 100 ° C. to 250 ° C. is preferably contained in 10% to 80% of the total solvent.

Examples of the solvent (W1) containing a hydroxyl group having a boiling point of 100 ° C to 250 ° C include 1-methoxy-2-propanol (boiling point 118 ° C to 119 ° C), ethyl lactate (boiling point 155 ° C), 1,3-butanediol ( Boiling point 203 ° C. to 204 ° C.), 1,3-butylene glycol (boiling point 203 ° C. to 204 ° C.), 2-methyl-1,3-propanediol (boiling point 123 ° C. to 125 ° C.), 3-methyl-1,3- Butanediol (boiling point 203 ° C. to 205 ° C.), 3-methoxy-3-methyl-1-butanol (173 ° C. to 175 ° C.), 3-methoxybutanol (boiling point 161 ° C.) n-butyl alcohol (boiling point 118 ° C.), isobutyl Alcohol (boiling point 108 ° C), cyclohexanol (boiling point 161 ° C), diacetone alcohol (boiling point 168 ° C), benzyl alcohol (boiling point 20 ° C) ° C.), mentioned and methyl cyclohexanol (boiling point 171 ° C. to 173 ° C.), especially in terms of contrast ratio, 1-methoxy-2-propanol, ethyl lactate, 3-methoxy butanol is preferred.
Further, two or more kinds can be used in combination without being limited to the above-mentioned solvent.

  A solvent can be used in the quantity of 100-10000 weight part with respect to 100 weight part of coloring agents in a coloring composition, Preferably it is 500-5000 weight part.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The content of the photopolymerizable monomer is preferably 5 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 400 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether Or a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p- Toxiphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoylo Shim)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 5 to 400 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Among the sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like is used.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
By using polyfunctional thiol together with the above-mentioned photopolymerization initiator, in the radical polymerization process after light irradiation, it acts as a chain transfer agent and generates a thiyl radical that is less susceptible to polymerization inhibition by oxygen. The composition becomes highly sensitive. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate) ), Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s- Examples include triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine.
These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the colorant.
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Ultraviolet absorber, polymerization inhibitor>
The coloring composition for a color filter of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino].
These ultraviolet absorbers can be used singly or in combination of two or more at any ratio as required.

Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenolic compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine Nitroso compounds and their ammonium salts or aluminum salts and the like.
These polymerization inhibitors can be used singly or as a mixture of two or more at any ratio as required.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.
By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

<Antioxidant>
The colored composition for a color filter of the present invention can contain an antioxidant in order to increase the transmittance of the coating film. The antioxidant prevents the photopolymerization initiator contained in the coloring composition for the color filter from being oxidized and yellowing due to a thermal process during thermal curing or ITO annealing, so that the transmittance of the coating film can be increased. it can. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

Preferable antioxidants include hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, sulfide antioxidants, and the like. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.
These antioxidants can be used singly or in combination of two or more at any ratio as required.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5- And di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate.

  In the hindered amine antioxidant, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N , N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4- Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3,4 -Butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6- Tetramethyl-4-piperidyl) Mino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2,2 , 6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) -4 Polycondensate with -hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2, 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine and the like.

  As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine- 6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2- Yl) oxy] ethyl] amine and ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl).

  As sulfide-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like.

The content of the antioxidant is preferably used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the solid content of the color filter coloring composition.
When the amount of the antioxidant is less than 0.1% by weight, the effect of increasing the transmittance is small.

<Other ingredients>
The coloring composition for a color filter of the present invention contains an adhesion improver such as a silane coupling agent or an amine compound that has a function of reducing dissolved oxygen in order to improve adhesion to a transparent substrate. Can be made.

  Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  The silane coupling agent can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 -2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl paratoluidine, etc. are mentioned.

<Method for producing colored composition for color filter>
The coloring composition for a color filter of the present invention comprises a kneader, a coloring agent in a coloring agent carrier such as a resin and / or a solvent, if necessary, together with a dispersing aid, using a dispersing agent (X). It can be produced by finely dispersing using various dispersing means such as a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed.
The epoxy compound may be added at the stage of preparing the colorant dispersion, and the same effect can be obtained even if it is added later to the prepared colorant dispersion.
When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need. In this case, the dispersant (X) can be used by simply adding and mixing it with a colorant solution in which a dye or the like is dissolved.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, not only the dispersant but also a dispersion aid such as a pigment derivative and a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment on a substrate, and further includes a magenta filter segment, a cyan filter segment, or a yellow filter segment. Alternatively, the at least one filter segment is formed from the coloring composition of the present invention.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate, the contrast of the liquid crystal display panel can be further increased. As the black matrix, chromium, a chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used. However, the present invention is not limited thereto, and the coloring composition for color filters of the present invention A black matrix formed from is preferable. A thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment and / or the black matrix on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the color composition for color filter prepared as a color composition for solvent development type or alkali development type color filter is dried on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It is applied so that the film thickness is 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase UV exposure sensitivity, after applying and drying the above color filter coloring composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. Ultraviolet exposure can also be performed after forming a film.

  An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed on the color filter as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAc” means propylene glycol monomethyl ether acetate.

  The weight average molecular weight (Mw) of the resin, the ammonium salt value of the resin having a cationic group in the side chain, and the measurement method of the average primary particle diameter of the pigment are as follows.

<Weight average molecular weight (Mw) of resin>
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent. It is a weight average molecular weight (Mw).

<Average primary particle diameter of pigment>
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

<Specific surface area of pigment>
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

<Contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

First, the used pigment derivative will be described.
<Structural formula of pigment derivative>

First, the used pigment derivative will be described.
<Structural formula of pigment derivative>
Table 2 summarizes the basic skeleton and terminal skeleton of the derivatives having basic substituents used, and appends the structural formula of the organic pigment residue. The structural formula of the derivative is obtained by replacing the amine group bonded to the organic pigment residue with the terminal skeleton in Table 2.

Formula (53):

Formula (54):

Formula (55):

[In the general formulas (53) to (55),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
n is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenylene group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R. ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. An alkenyl group having 20 carbon atoms and an arylene group having 6 to 20 carbon atoms which may have a substituent, and R ⁵⁶ is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms which may have a substituent. An alkenyl group having 2 to 20 carbon atoms, which may have
R ⁵⁷ is a substituent represented by the general formula (53) or a substituent represented by the general formula (54);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the above general formula (53), or a substituent represented by the above general formula (54). ]

General formula (60)

General formula (61)

Formula (62)

General formula (63)

General formula (64)

General formula (65)

Formula (66)

General formula (67)

General formula (68)

  Then, the manufacturing method of the acrylic resin solution used for the Example and the comparative example, the resin-type dispersant solution, the refinement | purification pigment, the pigment dispersion, the green photosensitive coloring composition, and the blue photosensitive coloring composition is demonstrated.

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution)
A reactor equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of PGMAc, heated to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 2 , 2′-Azobisisobutyronitrile (0.4 parts) was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. To prepare an acrylic resin solution.
<Method for producing dispersant>
(Synthesis of dispersant (XC-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, 0.12 part of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 part of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added at 120 ° C. For 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (XC-1) having an acid value of 43 and a weight average molecular weight of 9000.

(Synthesis of dispersant (Xa-1))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50 parts of methyl methacrylate, 50 parts of t-butyl methacrylate, and 45.4 parts of PGMAc and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70 ° C., 6 parts of 3-mercapto-1,2-propanediol was added, 0.12 part of AIBN (azobisisobutyronitrile) was further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by solid content measurement. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 part of DBU (1,8-diazabicyclo- [5.4.0] -7-undecene) as a catalyst were added at 120 ° C. For 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (Xa-1) having an acid value of 43 and a weight average molecular weight of 9000.

(Synthesis of dispersant (Xa-2 to 4))
Dispersants (Xa-2 to 4) were synthesized in the same manner as the dispersant (Xa-1) except that the raw materials shown in Table 3 were changed.

The abbreviations in Table 3 are as follows.
<< ethylenically unsaturated monomer (c) >>
MMA: methyl methacrylate n-BA: n-butyl acrylate

[Ethylenically unsaturated monomer having thermally crosslinkable group]
t-BA: tert-butyl acrylate OXMA: “ETERRNACOLL OXMA” manufactured by Ube Industries
(3-Methyl-3-oxetanyl) methyl methacrylate MOI-BM: “Karenz MOI-BM” manufactured by Showa Denko
Methacrylic acid 2-([1′-methylpropylideneamino] carboxyamino) ethyl

AIBN: 2,2′-azobisisobutyronitrile PMA: pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.)
TMA: Trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.)
DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene (manufactured by Sun Apro Co., Ltd.)

(Synthesis of dispersant (Xa-5))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 part of monobutyltin oxide, PGMAc88. Nine parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and hydroxymethyl 20 parts of methacrylate was charged, 0.12 part of AIBN and 26.8 parts of PGMAc were added, and the reaction was performed for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. PGMAc was added to adjust the non-volatile content to 50% to obtain a dispersant (Xa-5) having an acid value of 43 and a weight average molecular weight of 9000.

(Synthesis of dispersant (Xa-6))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 part of monobutyltin oxide, PGMAc88. Nine parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and hydroxymethyl 20 parts of methacrylate was charged, 0.12 part of AIBN and 26.8 parts of PGMAc were added, and the reaction was performed for 10 hours. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed. Furthermore, 23.9 parts of MOI (2-methacryloyloxyethyl isocyanate) and 0.04 part of hydroquinone were charged, and the reaction was performed until the disappearance of the peak at 2270 cm −1 based on the isocyanate group was confirmed by IR. After confirming the disappearance of the peak, the reaction solution was cooled and adjusted to 50% non-volatile content with PGMAc to obtain a dispersant (Xa-6) having an unsaturated double bond equivalent 907, an acid value 43, and a weight average molecular weight 9500. .

<Production method of fine pigment>
<Method for producing red colorant>
(Production of Red Colorant 1 (R-1): Azo Compound 1)
Below, the specific synthesis method of the said azo compound 1 is shown with the reaction scheme (the following reaction scheme A). Other azo compounds according to the present invention can be synthesized according to a similar scheme. In addition, the manufacturing method (synthesis method) of an azo compound is not limited to the following method.

<< Synthesis of Compound (B) >>
To 573 parts of toluene, 90 parts of 2,3-hydroxynaphthoic acid and 1.2 parts of N, N-dimethylformamide were added, heated to 85 ° C., and 556.3 parts of thionyl chloride was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was refluxed for 1 hour. The above reaction solution was added dropwise over 30 minutes to a solution in which 80.9 parts of separately prepared compound (A) and 264 parts of toluene were heated to 85 ° C., and the mixture was heated to reflux for 2 hours. After cooling this reaction liquid to 95 ° C., 8.0 parts of 28% ammonia aqueous solution and 20 parts of water were added and stirred at 95-100 ° C. for 15 minutes, and then toluene and unreacted compound (A) were removed by steam distillation. did. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 152 parts (yield: 95.8%) of compound (B).

<< Synthesis of Azo Compound 1 >>
After adding 36.3 parts of Compound (C) to 252.2 parts of glacial acetic acid, 39.1 parts of 35% hydrochloric acid was added and cooled to −2 to 0 ° C. After adding 42.2 parts of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0-5 ° C. This reaction solution was added to a mixed solution consisting of 50.7 parts of the compound (B) prepared separately by the previous method, 67.1 parts of 25% sodium hydroxide solution, 772 parts of water and 680 parts of isopropyl alcohol for 15 minutes. It was dripped at. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining at 80 ° C. The precipitated reaction product was collected by filtration, washed with hot water and methanol, and dried to obtain 85.9 parts of azo dye 1. (
Yield: 98%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 1.

  Next, 80 parts of the azo compound 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 1 (R-1) were obtained. The average primary particle size was 38 nm.

(Production of red colorant 2 (R-2): azo compound 2)
(Synthesis of Azo Compound 2)
Red colorant 1 (R—) was used except that 66.8 parts of 3-aminobenztrifluoride was used instead of 80.9 parts of compound (A) used in the production of red colorant 1 (R-1). The same operation as in the production of 1) was performed to obtain 80.0 parts (yield 98%) of azo compound 2. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 2.

  Next, 80 parts of the azo compound 2, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 2 (R-2) were obtained. The average primary particle size was 42 nm.

(Production of Red Colorant 3 (R-3): Azo Compound 3)
(Synthesis of Azo Compound 3)
Red except that 34.9 parts of 3-amino-4-methoxybenzanilide used in the production of red colorant 1 (R-1) was used, except that 24.9 parts of 3-amino-4-methoxybenzamide were used. Operation similar to manufacture of the coloring agent 1 (R-1) was performed, and 80.0 parts (yield 97%) of azo compounds 3 were obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 3.

  Next, 80 parts of the azo compound 3, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 3 (R-3) were obtained. The average primary particle size was 45 nm.

(Production of Red Colorant 4 (R-4): Azo Compound 4)
(Synthesis of Azo Compound 4)
Instead of 80.9 parts of compound (A) used in the production of red colorant 1 (R-1), 66.8 parts of 3-aminobenztrifluoride, and 3-amino-4-methoxybenzanilide Instead, except that 24.9 parts of 3-amino-4-methoxybenzamide were used, the same operation as in the production of red colorant 1 (R-1) was performed, and 80.0 parts of azo compound 4 (yield) 97%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 4.

  Next, 80 parts of the azo compound 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 4 (R-4) were obtained. The average primary particle size was 39 nm.

(Production of Red Colorant 5 (R-5): Azo Compound 5)
(Synthesis of Azo Compound 5)
Instead of compound (A) used in the preparation of red colorant 1 (R-1), 66.8 parts 2-aminobenztrifluoride, and 3 instead of 3-amino-4-methoxybenzanilide Except for using 24.9 parts of -amino-4-methoxybenzamide, the same operation as in the production of red colorant 1 (R-1) was performed to obtain 80.0 parts of azo compound 5 (yield 95%). It was. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 5.

  Next, 80 parts of the azo compound 5, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 5 (R-5) were obtained. The average primary particle size was 38 nm.

(Production of Red Colorant 6 (R-6): Azo Compound 6)
(Synthesis of Azo Compound 6)
Instead of compound (A) used in the production of red colorant 1 (R-1), instead of 5-chloro-2-aminobenztrifluoride and 3-amino-4-methoxybenzanilide, 3- Except for using 24.9 parts of amino-4-methoxybenzamide, the same operation as in the production of Red Colorant 1 (R-1) was performed to obtain 80.0 parts of azo compound 6. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 6.

  Next, 80 parts of the azo compound 6, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 6 (R-6) were obtained. The average primary particle size was 42 nm.

(Production of Red Colorant 7 (R-7): Azo Compound 7)
(Synthesis of Azo Compound 7)
95.1 parts of 3,5-bis (trifluoromethyl) aniline and 3-amino-4-methoxybenzanilide instead of compound (A) used in the production of red colorant 1 (R-1) Instead of using 24.9 parts of 3-amino-4-methoxybenzamide, the same operation as in the production of red colorant 1 (R-1) was carried out, and 80.0 parts of azo compound 7 (yield) was obtained. Rate 96%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 7.

  Next, 80 parts of the azo compound 7, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 7 (R-7) were obtained. The average primary particle size was 47 nm.

(Production of Red Colorant 8 (R-8): Azo Compound 8)
(Synthesis of Azo Compound 8)
Instead of the compound (A) used in the production of the red colorant 1 (R-1), 0.050 mol amount of 4-fluoro-3-aminobenztrifluoride, and 3-amino-4-methoxybenzanilide Instead, except that 0.015 mol amount of 3-amino-4-methoxybenzamide was used, the same operation as in the production of red colorant 1 (R-1) was performed, and 7.97 g of azo compound 8 (yield 96) %)Obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 8.

  Next, 80 parts of the azo compound 8, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 8 (R-8) were obtained. The average primary particle size was 42 nm.

(Production of Red Colorant 9 (R-9): Azo Compound 9)
(Synthesis of Azo Compound 9)
Instead of the compound (A) used in the production of the red colorant 1 (R-1), 74.3 parts of 2-chloro-5-aminobenztrifluoride, and 3-amino-4-methoxybenzanilide Instead, except that 24.9 parts of 3-amino-4-methoxybenzamide were used, the same operation as in the production of red colorant 1 (R-1) was performed, and 80.0 parts of azo compound 9 (yield) 97%). As a result of mass spectrometry by TOF-MS, it was identified as azo compound 9.

  Next, 80 parts of the azo compound 9, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 9 (R-9) were obtained. The average primary particle size was 41 nm.

(Production of Red Colorant 10 (R-10): Azo Compound 10)
(Synthesis of Azo Compound 10)
Instead of compound (A) used in the preparation of red colorant 1 (R-1), 66.8 parts 4-aminobenztrifluoride, and 3 instead of 3-amino-4-methoxybenzanilide Except for using 24.9 parts of -amino-4-methoxybenzamide, the same operation as in the production of red colorant 1 (R-1) was performed to obtain 80.0 parts of azo compound 10 (yield 95%). It was. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 10.

  Next, 80 parts of the azo compound 10, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 10 (R-10) were obtained. The average primary particle size was 48 nm.

(Production of red colorant 11 (R-11): azo compound 11)
(Synthesis of Azo Compound 11)
Instead of 3-amino-4-methoxybenzanilide used in the production of red colorant 1 (R-1), red colorant 1 (except for using 24.9 parts of 3-amino-4-methylbenzamide) The same operation as in the production of R-1) was carried out to obtain 80.0 parts (yield 97%) of azo compound 11. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 11.

  Next, 80 parts of the azo compound 11, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 11 (R-11) were obtained. The average primary particle size was 50 nm.

(Production of Red Colorant 12 (R-12): Azo Compound 12)
(Synthesis of Azo Compound 12)
Instead of 3-amino-4-methoxybenzanilide used in the production of red colorant 1 (R-1), 3-amino-4-methoxybenz- (2′-chloro-5′-trifluoromethyl) anilide Was used in the same manner as in the production of the red colorant 1 (R-1), and 80.0 parts (yield 96%) of the azo compound 12 was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 12.

  Next, 80 parts of the azo compound 12, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 12 (R-12) were obtained. The average primary particle size was 38 nm.

(Production of Red Colorant 13 (R-13): Azo Compound 13)
(Synthesis of Azo Compound 13)
Instead of compound (A) used in the preparation of red colorant 1 (R-1), 66.8 parts 3-aminobenztrifluoride and 3 amino-3 instead of 3-amino-4-methoxybenzanilide Except for using 46.5 parts of -amino-4-methoxybenz- (3'-trifluoromethyl) anilide, the same operation as in the production of red colorant 1 (R-1) was performed, and azo compound 13 was converted to 80 0.0 part (yield 95%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 13.

  Next, 80 parts of the azo compound 13, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 13 (R-13) were obtained. The average primary particle size was 36 nm.

(Production of Red Colorant 14 (R-14): Azo Compound 14)
(Synthesis of Azo Compound 14)
Red colorant 1 (R-1) was used except that 44.7 parts of the following compound (D) was used instead of 3-amino-4-methoxybenzanilide used in the production of red colorant 1 (R-1). ) To give 80.0 parts (95% yield) of azo compound 14. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 14.

  Next, 80 parts of the azo compound 14, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 14 (R-14) were obtained. The average primary particle size was 40 nm.

Compound (D)

(Production of Red Colorant 15 (R-15): Azo Compound 15)
(Synthesis of Azo Compound 15)
Instead of (A) used in the preparation of red colorant 1 (R-1), 66.8 parts 3-aminobenztrifluoride and instead of 3-amino-4-methoxybenzanilide, compound ( Except for using 44.7 parts of D), the same operation as in the production of red colorant 1 (R-1) was performed to obtain 80.0 parts (yield 97%) of azo compound 15. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 15.

  Next, 80 parts of the azo compound 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 15 (R-15) were obtained. The average primary particle size was 43 nm.

(Production of Red Colorant 16 (R-16): Azo Compound 16)
(Synthesis of Azo Compound 16)
Red Colorant 1 (R) except that 27.0 parts of 3-amino-N-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in the production of Red Colorant 1 (R-1). The same operation as in the preparation of R-1) was performed to obtain 80.0 parts (yield 97%) of azo compound 16. As a result of mass spectrometry by TOF-MS, it was identified as azo compound 16.

  Next, 80 parts of the azo compound 16, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 16 (R-16) were obtained. The average primary particle size was 43 nm.

(Production of Red Colorant 17 (R-17): Azo Compound 1 Refined by Acid Pasting Method)
Add 80 parts of azo compound 1 obtained in the production of red colorant 1 (R-1) to 1200 parts of concentrated sulfuric acid, stir at 40 ° C. for 3 hours, and then inject this sulfuric acid solution into 24000 parts of cold water at 3 ° C. did. The produced precipitate was filtered, washed with water, and dried overnight at 80 ° C. to obtain 78 parts of red colorant 17 (R-17). The average primary particle size was 65 nm.

(Production of Red Colorant 18 (R-18): Azo Compound 1 / PR176)
125 parts of 3-amino-4-methoxybenzanilide are dispersed in 2000 parts of water, ice is added to adjust the temperature to 5 ° C., 205 parts of 35% aqueous hydrochloric acid is added, and the mixture is stirred for 1 hour. A water solution prepared by adding 110 parts to water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 380 parts of an 80% aqueous acetic acid solution, 418 parts of a 25% aqueous sodium hydroxide solution, and 413 parts of water was added to form an aqueous diazonium salt solution.
Meanwhile, 154 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-
Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboxamide 33
. 5 parts and 1344 parts of a 25% aqueous sodium hydroxide solution were dissolved in 3500 parts of methanol to obtain a coupler solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours. The azo pigment of azo compound 1 and the azo compound represented by the general formula (6) C. a pigment. I. 309 parts of a mixture with Pigment Red 176 were obtained. As a result of mass spectrometry by TOF-MS, an azo pigment of azo compound 1 and C.I. I. It was confirmed that the mass ratio of the pigment red 176 mixture of naphthol azo pigments was 82.1: 17.9.

  A red colorant 18 (R-18) was obtained from the obtained azo compound by the same salt milling method as that for the red colorant 1 (R-1). The average primary particle size was 32 nm.

<Method for producing other red colorant>
(Production of red colorant 19 (RC-1): PR254)
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) ("Irgaphore Red B-CF" manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 6 ° C. The mixture was kneaded for a time and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 19 (RC-1) were obtained. The average primary particle size was 33 nm.

(Production of red colorant 20 (RC-2): PR177)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Pigment Red 177 (PR177) (“CROMOPHTALRED A2B” manufactured by BASF) was used in the same manner as in the production of Red Colorant 1 (RC-1) to obtain 97 parts of Red Colorant 20 (RC-2). It was. The average primary particle size was 37 nm.

(Production of red colorant 21 (RC-3): PR242)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Pigment Red 242 (PR242) ("Sando" manufactured by Clariant
rinScallet4RF ") except that the red colorant 1 (RC-1) was produced, and 98 parts of red colorant 21 (RC-3) was obtained. The average primary particle size was 39 nm.

(Production of red colorant 22 (RC-4): PR176)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Pigment Red 176 (PR176) (“Novoperm Carmine HF3C” manufactured by Clariant) was used in the same manner as in the production of Red Colorant 1 (RC-1), and 98 parts of Red Colorant 22 (RC-4) were used. Obtained. The average primary particle size was 35 nm.

(Production of red colorant 23 (RC-5): PO38)
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by BASF) I. Pigment Orange 38 (PO38) (“Novoperm Red HF part” manufactured by Clariant) was performed in the same manner as in the production of Red Colorant 1 (RC-1), and 97 parts of Red Colorant 23 (RC-5) Got. The average primary particle size was 39 nm.

(Production of Red Colorant 24 (RC-6): Formula (2-19))
(Brominated diketopyrrolopyrrole pigment formula (2-19))
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued for 2 hours at 90 ° C. to obtain an alkali metal salt of a diketopyrrolopyrrole compound. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser and rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole compound obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole compound at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the resulting diketopyrrolopyrrole compound aqueous paste was filtered off with an ultrafiltration machine, dried at 80 ° C. for 24 hours, and pulverized, thereby bromination represented by the formula (2-19). 150.8 parts of diketopyrrolopyrrole pigment were obtained.

100 parts of the brominated diketopyrrolopyrrole pigment represented by the formula (2-19) obtained above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) at 60 ° C. And kneaded for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 24 (RC-6) were obtained. The average primary particle size was 45 nm.

<Manufacturing method of other colorants>
(Production of green colorant 1: PG58)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (“FASTOGENGREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The product was put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, then dried overnight at 85 ° C., 190 parts of A green colorant 1 was obtained, and the specific surface area of the green colorant 1 was 75 m ² / g.

(Production of yellow colorant 1: PY138)
Quinophthalone yellow pigment C.I. I. 500 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 490 parts of yellow colorant 1 were obtained. The specific surface area of the yellow colorant 1 was 85 m ² / g.

(Preparation of blue colorant 1: PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue colorant 1 were obtained. The specific surface area of the blue colorant 1 was 80 m ² / g.

(Preparation of purple colorant 1: PV23)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of purple colorant 1 were obtained. The specific surface area of the purple colorant 1 was 95 m ² / g.

<Method for producing pigment dispersion>
(Pigment dispersion (DC-1): PR254)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-1) whose non-volatile component is 20 weight% was produced.
Red colorant 19 (RC-1): 11.0 parts (CI Pigment Red 254)
Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Dispersant solution (dispersant Xa-1): 5.0 parts

(Pigment dispersion (DC-2): PR177)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-2) whose non-volatile component is 20 weight% was produced.
Red colorant 20 (RC-2): 11.0 parts (CI Pigment Red 177)
Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Dispersant solution (dispersant Xa-1): 5.0 parts

(Pigment dispersion (DC-3): PR242)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-3) whose non-volatile component is 20 weight% was produced.
Red colorant 21 (RC-3): 11.0 parts (CI Pigment Red 242)
Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Dispersant solution (dispersant Xa-1): 5.0 parts

(Pigment dispersion (DC-4): PR176)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-4) whose non-volatile component is 20 weight% was produced.
Red colorant 22 (RC-4): 11.0 parts (CI Pigment Red 176)
Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution ("EFKA4300" manufactured by BASF): 5.0 parts

(Pigment dispersion (DC-5): PO38)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-5) whose non-volatile component is 20 weight% was produced.
Red colorant 23 (RC-5): 11.0 parts (CI Pigment Orange 38)
Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution ("EFKA4300" manufactured by BASF): 5.0 parts

(Pigment dispersion (DC-6): Brominated diketopyrrolopyrrole pigment formula (2-19))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-6) whose non-volatile component is 20 weight% was produced.
Red colorant 24 (RC-6): 11.0 parts (brominated diketopyrrolopyrrole pigment formula (2-19))
Acrylic resin solution: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution ("EFKA4300" manufactured by BASF): 5.0 parts

Table 4 shows pigment dispersions using other red colorants.

<Green photosensitive coloring composition, blue photosensitive coloring composition production method>
(Green photosensitive coloring composition 1: PG58 / PY138)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A green pigment dispersion having a nonvolatile content of 20% by weight was prepared.
Green colorant 1 (CI Pigment Green 58): 11.0 parts acrylic resin solution: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts resin type dispersant solution ("EFKA4300" manufactured by BASF) ]): 5.0 parts

The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A yellow pigment dispersion having a nonvolatile content of 20% by weight was prepared.
Yellow Colorant 1 (CI Pigment Yellow 138): 11.0 parts acrylic resin solution: 31.2 parts propylene glycol monomethyl ether acetate (PGMAC): 50.9 parts resin-type dispersant solution (“EFKA4300 manufactured by BASF Corporation) ]): 6.9 parts

Subsequently, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition 1.
Green pigment dispersion: 32.0 parts Yellow pigment dispersion: 18.0 parts Acrylic resin solution: 7.5 parts Photopolymerizable monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.): 2.0 parts Pentaerythritol hexaacrylate photopolymerization initiator (“OXE-02” manufactured by BASF): 1.5 parts Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]- , 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1: PB15: 6 / PV23)
The non-volatile content is 20% by weight in the same manner as the green pigment dispersion except that the green colorant 1 (CI Pigment Green 58) is changed to the blue colorant 1 (CI Pigment Blue 15: 6). Of blue pigment dispersion was obtained.

  Purple with a non-volatile content of 20% by weight in the same manner as the green pigment dispersion, except that the green colorant 1 (CI Pigment Green 58) was changed to the purple colorant 1 (CI Pigment Violet 23). A pigment dispersion was obtained.

  Subsequently, 30.0 parts of the green pigment dispersion and 18.0 parts of the yellow pigment dispersion were replaced with a total of 50.0 parts of 46.0 parts of the blue dispersion and 4.0 parts of the purple dispersion. A blue photosensitive coloring composition 1 was obtained in the same manner as in the green photosensitive coloring composition 1 except for the above.

[Example 1]
(Pigment dispersion (D-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (D-1) whose non-volatile component is 20 weight% was produced.
Red colorant: Red colorant 1 (R-1): 10.0 parts
Binder resin: Acrylic resin solution: 35.0 parts Solvent: Propylene glycol monomethyl ether acetate (PGMAc): 49.0 parts Resin type dispersant: Dispersant solution (dispersant Xa-1): 5.0 parts Derivative: (derivative A): 1.0 part

[Examples 2-34, Comparative Examples 1-6]
(Pigment dispersion (D-2 to 34, 37 to 42))
Hereinafter, the pigment dispersions (D-2 to 34, 37 to 42) are the same as the pigment dispersion (D-1) except that the red colorant, the resin-type dispersant, and the derivatives are changed to the compositions shown in Table 4. Adjusted.

[Example 35]
(Pigment dispersion (D-35))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (D-35) having a non-volatile component of 20% by weight was produced.
Red colorant: Red colorant 1 (R-1): 10.0 parts
Binder resin: Acrylic resin solution: 35.0 parts Solvent: Propylene glycol monomethyl ether acetate (PGMAc): 29.1 parts 3-methoxybutanol: 19.9 parts Resin type dispersant: Dispersant solution (dispersant Xa-1) : 5.0 parts Derivative: (Derivative A): 1.0 part

[Example 36]
(Pigment dispersion (D-36))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (D-35) having a non-volatile component of 20% by weight was produced.
Red colorant: Red colorant 1 (R-1): 10.0 parts
Binder resin: Acrylic resin solution: 35.0 parts Solvent: Propylene glycol monomethyl ether acetate (PGMAc): 9.2 parts 3-methoxybutanol: 39.8 parts Resin type dispersant: Dispersant solution (dispersant Xa-1) : 5.0 parts Derivative: (Derivative A): 1.0 part

[Evaluation of coloring composition (pigment dispersion) for color filter]
The viscosity characteristics, color characteristics, and contrast ratio of the pigment dispersions (D-1 to 42) obtained in Examples and Comparative Examples were evaluated by the following methods. Table 6 shows the evaluation results.

<Viscosity characteristics>
As for the viscosity of the pigment dispersion, an initial viscosity at 25 ° C. was measured using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity.

A: When the rate of change in viscosity is within ± 5% and no sediment is formed.
○: When the viscosity change rate is within ± 10% and no sediment is formed.
(Triangle | delta): When a viscosity change rate is less than +/- 10-20% and a sediment was not produced.
X: When the viscosity change rate exceeds ± 20%, or when a precipitate is generated even when the viscosity change rate is within ± 20%.

<Color characteristic evaluation>
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, so that the chromaticity of the substrate is x = 0. A coated substrate was obtained such that 640, y = 0.322. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
Using the obtained pigment dispersion, a spin coater was used to produce three coated substrates so that the dry film thickness was about 1 μm by changing the number of rotations. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method.

The coloring composition for a color filter of the present invention comprising a coloring agent containing the naphtholazo pigment [A1] represented by the general formula (1) and a dispersant (X) having a thermally crosslinkable group is a coloring composition of a comparative example. As a result, the viscosity was low and the brightness and CR were high. In particular, the naphthol azo pigment [A1] of the coloring composition of the present invention is an existing pigment C.I. I. Compared to Pigment Orange 38, C.I. I. Pigment Red 254, bluer, C.I. I. It is yellowish than CI Pigment Red 177, and the rising wavelength of the transmission spectrum is in the range of 570 to 590 nm. Therefore, it effectively acts on the bright line of the backlight generally used in liquid crystal display devices, and high brightness is obtained. It was. Further, by using the naphtholazo pigment and the dispersant (X) in combination, the pigment can be stably present in a primary particle state, and a high contrast ratio can be obtained at the same time.

[Example 40]
(Photosensitive coloring composition (DR-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive colored composition (DR-1).
(Pigment dispersion) (Total 50 parts)
Pigment dispersion (D-1): 20.0 parts Pigment dispersion (RC-1): 30.0 parts Acrylic resin solution: 7.5 parts Photopolymerizable monomer (“Aronix M-402 manufactured by Toagosei Co., Ltd.) ]) 2.0 parts dipentaerythritol hexaacrylate photoinitiator ("OXE-02" manufactured by BASF): 1.5 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

[Examples 41 to 81, Comparative Examples 7 to 10]
(Photosensitive coloring composition (DR-2 to 46))
A photosensitive colored composition (DR-2 to 46) was obtained in the same manner as the photosensitive colored composition (DR-1) except that the pigment dispersion was changed to the type and blending amount of the pigment dispersion shown in Table 7. . In each photosensitive coloring composition adjustment, it added so that the sum total of a pigment dispersion might be 50 parts, and adjusted 100 parts of photosensitive coloring compositions.

[Evaluation of Color Filter Coloring Composition (Photosensitive Coloring Composition)]
The brightness, contrast, heat resistance, and solvent resistance of the photosensitive coloring compositions (DR-1 to 46) obtained in Examples and Comparative Examples were measured by the following methods. Table 8 shows the evaluation results.

<Color characteristic evaluation>
The photosensitive coloring composition (DR1 to 46) is applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and then dried at 70 ° C. for 20 minutes, using an ultrahigh pressure mercury lamp. Then, UV exposure was performed with an integrated light quantity of 150 mJ / cm ² , development was performed with an alkaline developer at 23 ° C., and then heated and allowed to cool at 230 ° C. for 60 minutes to obtain a coated substrate. After heat treatment at 230 ° C., a coated substrate having x = 0.658 and y = 0.325 in a C light source was obtained. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
An evaluation substrate was prepared in the same manner as the color characteristic evaluation of the coating film. The CR of the obtained coated substrate was measured.

(NMP resistance and heat resistance of coating film)
The resulting photosensitive colored resist material was evaluated for NMP resistance and coating film heat resistance by the following methods.
In addition, the film thickness of the coating film was measured using Dektak 3030 (made by Nippon Vacuum Technology Co., Ltd.).

  In the evaluation of NMP resistance and heat resistance, after applying a resist material, UV exposure is performed through a mask having a specific pattern, and then an alkali developer is sprayed to remove the uncured portion to form a specific pattern. doing. This specific pattern is a stripe pattern in which linear patterns are arranged, the pattern width is 200 μm, and the distance between the patterns is also 200 μm.

(Evaluation of coating NMP resistance)
After applying the resist material obtained so that the dry coating film becomes about 2.5 μm on the transparent substrate, and exposing to ultraviolet rays through the mask having the above-mentioned stripe pattern, the alkali developer is sprayed by spraying. The uncured part was removed to form a stripe pattern. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Here, after measuring the chromaticity (L * (1), a * (1), b * (1)) with C light source, it was immersed in NMP (N-methylpyrrolidone) for 30 minutes, and further with C light source. Was measured (L * (2), a * (2), b * (2)).
Using the color difference values before and after NMP immersion, the color difference ΔE * ab was calculated according to the following formula, and the heat resistance of the coating film was evaluated in the following three stages.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

◎: ΔE * ab is 1 or less ○: ΔE * ab is greater than 1 and less than 3 ×: ΔE * ab is 3 or more

(Evaluation of heat resistance of coating film)
After applying the resist material obtained so that the dry coating film becomes about 2.5 μm on the transparent substrate, and exposing to ultraviolet rays through the mask having the above-mentioned stripe pattern, the alkali developer is sprayed by spraying. The uncured part was removed to form a stripe pattern. Thereafter, it was baked in an oven at 230 ° C. for 20 minutes. Thereafter, an ITO (indium tin oxide) film was formed by sputtering so as to have an average film thickness of 1500 angstroms. Using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), the chromaticity 1 (L * (1), a * (1), b * (1)) of the obtained coating film with a C light source Measured. Further, as a heat resistance test, the sample was heated in an oven at 230 ° C. for 3 hours, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured. Using the measured color difference value, the color difference ΔE * ab was calculated according to the following formula, and the heat resistance of the coating film was evaluated.

ΔE * ab = [[L * (2) −L * (1)] ² + [a * (2) −a * (1)] ² + [b * (2) −b * (1)] ² ] ^1/2

◎: ΔE * ab is 1 or less ○: ΔE * ab is greater than 1 and less than 3 ×: ΔE * ab is 3 or more

The coloring composition for a color filter of the present invention containing the colorant containing the naphtholazo pigment [A1] represented by the general formula (1) and the dispersant (X) having a thermally crosslinkable group is both lightness and CR And the results of heat resistance and solvent resistance were good.

[Example of color filter production]
Using the red photosensitive coloring composition 1, the green photosensitive coloring composition 1 and the blue photosensitive coloring composition 1 of the present invention, the dry film thickness is 1.7 μm by spin coating on the substrate. It is applied, dried, and exposed to UV light through a mask having a predetermined pattern provided in a non-contact state with the coating film. After that, an alkaline developer is sprayed to remove the uncured portion and form a desired pattern. After that, it was heated at 230 ° C. for 1 hour. By repeating the same operation for green and blue to produce a color filter, it was possible to produce an RGB three-color filter with high brightness and excellent resistance.

Claims (5)

A color filter coloring composition containing a colorant, a dispersant (X), a binder resin, and a solvent (W),
The colorant contains a naphtholazo pigment [A1] represented by the following general formula (1), and the dispersant (X) is formed from a tetracarboxylic acid anhydride (b1) and a tricarboxylic acid anhydride (b2). A polyester portion X1 ′ having a carboxyl group, obtained by reacting an acid anhydride group in one or more acid anhydrides (b) selected with a hydroxyl group in the hydroxyl group-containing compound (a);
A coloring composition for a color filter, comprising a vinyl polymer portion X2 ′ obtained by radical polymerization of an ethylenically unsaturated monomer (c) and having a thermally crosslinkable functional group.

General formula (1)
[In General Formula (1), each A independently represents a hydrogen atom, a methyl group, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. Represents.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an _-SO 2 ^{NHR 12,} representative of at least one trifluoromethyl group among R 2 to R ^6. R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] The thermally crosslinkable functional group of the dispersant (X) is at least one selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, a blocked isocyanate group, and a (meth) acryloyl group. Item 2. A coloring composition for a color filter according to Item 1.   The coloring composition for a color filter according to claim 1 or 2, wherein the solvent (W) contains a solvent (W1) containing a hydroxyl group having a boiling point of 100C to 250C.   Furthermore, a photoinitiator is contained, The coloring composition for color filters of any one of Claims 1-3 characterized by the above-mentioned. A color filter comprising a filter segment formed from the colored composition for color filter according to any one of claims 1 to 4 on a substrate.