JP6733525B2 - Photosensitive coloring composition for color filter and color filter - Google Patents

Description

The present invention relates to a color liquid crystal display device, a pigment composition for a color filter used for manufacturing a color filter used for a color image pickup tube element, etc., and a color filter having a filter segment formed using the same. Is.

In the photosensitive composition for a color filter, a dispersant is generally used to keep the colorant in a good dispersed state, and a basic dispersant is used for a pigment having an acidic surface. The structure of the dispersant is often a structure-controlled one having a block structure or a comb structure. However, in the case of the block type, it is necessary to use a complicated polymerization method such as living radical polymerization (see Patent Document 1) for its production. In the case of a comb type, a comb tooth having a functional group such as a carboxyl group or an acryloyl group is grafted to a polyamine compound having a primary and/or secondary amine, and the remaining primary and/or There is a method (see Patent Documents 2 and 3) in which a secondary amine is used as a functional group that is adsorbed on the pigment surface.

Further, a method of maintaining a good dispersed state of a pigment by using a dispersant having an acidic functional group and a basic resin not having a structure control without using a dispersant having a structure control has been proposed. (See Patent Documents 4 to 6). However, the basic resin described here has high oil-solubility, but has very poor alkali developability (solubility in a developing solution) due to its poor fine developability and dispersion stability, resulting in poor alkali developability. Since the linearity defect and the shape defect of the derived pattern pixel have occurred, improvement of these various characteristics is strongly demanded.

Special table 2002-534542 gazette Japanese Patent Laid-Open No. 08-038875 JP, 08-143813, A JP-A-5-9405 JP, 10-338835, A JP, 2014-12813, A

The present invention aims to achieve the following objects. That is, an object of the present invention is to provide a photosensitive coloring composition which not only has low viscosity, storage stability, brightness and contrast, but also has excellent adhesion, developability, pattern linearity and pattern shape. , And to provide a color filter formed using the same.

The present inventors have conducted extensive studies in order to solve the above problems, when using a branched basic resin synthesized in the presence of a specific compound as a photosensitive coloring composition for a color filter, The inventors have found that a color filter having excellent dispersibility, stability, heat resistance, developability, and resolution can be produced, and completed the present invention.

That is, the present invention is a photosensitive coloring composition containing a colorant, a dispersant, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
An ethylenic dispersant containing an aromatic carboxyl group-containing resin (A) and an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of a trivalent or higher polyvalent mercaptan compound (s1) The present invention relates to a photosensitive coloring composition containing a basic resin (B) which is a polymer obtained by polymerizing an unsaturated monomer (b).

The present invention also relates to the above-mentioned photosensitive coloring composition, wherein the trivalent or higher polyvalent mercaptan compound (s1) is a thiocarboxylic acid derivative.

Further, in the present invention, the tertiary amino group in the ethylenically unsaturated monomer (b1) having a tertiary amino group is a group selected from the group consisting of a group represented by the following general formula (1) and a dialkylamino group. Which is the photosensitive coloring composition.

General formula (1)
[In the general formula (1),
R ²⁰¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR ²⁰³ ,
R ²⁰³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group,
R ²⁰² independently represents an alkyl group having 1 to 8 carbon atoms, and * represents a bond. ]

The present invention also relates to the above-mentioned photosensitive coloring composition, wherein the coloring agent is a halogenated phthalocyanine pigment.

Furthermore, the present invention relates to a color filter characterized by comprising a filter segment formed from the above-mentioned photosensitive coloring composition on a substrate.

The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a colorant, a dispersant, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the dispersant is an aromatic carboxyl group. An ethylenically unsaturated monomer (b) containing a group-containing resin (A) and an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of a trivalent or higher polyvalent mercaptan compound (s1) ) Is polymerized with the basic resin (B) to achieve not only low viscosity, storage stability, brightness and contrast, but also adhesion, developability, pattern linearity and pattern shape. It is characterized by doing.

Hereinafter, the present invention will be described in detail. In addition, in this application, when it describes with "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", it demonstrates especially. 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. Shall be represented. In addition, "CI" referred to in the present specification means color index (CI).

<Dispersant>
(Aromatic carboxyl group-containing resin (A))
The aromatic carboxyl group-containing resin (A) used in the present invention can be used without particular limitation as long as it has an aromatic carboxyl group in its molecule. A (meth)acrylic dispersant is particularly preferable. The weight average molecular weight of the resin is preferably 2,000 to 35,000, more preferably 4,000 to 25,000, further preferably 6,000 to 20,000, and particularly preferably 7,000 to 15,000. The acid value of the resin is preferably 5 to 200. It is more preferably 10 to 150, still more preferably 15 to 100, and particularly preferably 20 to 80. Among them, any of the following resins can be preferably used.

[Resin (a)]
The aromatic carboxyl group-containing resin (A) used in the present invention is a reaction between a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of an aromatic tricarboxylic acid anhydride and/or an aromatic tetracarboxylic acid dianhydride. It is preferably a resin which is a product. The resin (a) can be produced by a known method such as WO2008/007776. However, the polymer having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal, and a plurality of hydroxyl groups at the terminal are present. More preferably. For example, a preferable example of a polymer having two hydroxyl groups at one end is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. Obtainable. The hydroxyl group of the polymer having a hydroxyl group reacts with the acid anhydride group of the aromatic tricarboxylic acid anhydride and/or the aromatic tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and This produces an acid.

[Resin (b)]
The resin having an aromatic carboxyl group used in the present invention is a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of an aromatic tricarboxylic acid anhydride and/or an aromatic tetracarboxylic acid dianhydride. It is preferable that the resin is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a substance. The resin (b) can be produced by a known method such as JP 2010-185934 A. Among them, a hydroxyl group of a compound having two hydroxyl groups and one thiol group in the molecule, and an aromatic tricarboxylic acid. A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of an acid anhydride and/or an acid anhydride group of an aromatic tetracarboxylic dianhydride is preferable.

<<Compound having two hydroxyl groups and one thiol group in the molecule>>
Examples of the compound having two hydroxyl groups and one thiol group in the molecule of the present invention 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, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like can be mentioned.

<<Aromatic tricarboxylic acid dianhydride>>
The aromatic tricarboxylic acid dianhydride in the present invention may have any structure as long as it has one carboxylic acid anhydride group and one carboxylic acid group. 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. Acid anhydride (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid anhydride Etc.), 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' -Biphenyl tricarboxylic acid anhydride, 3,4,4'-biphenylmethane tricarboxylic acid anhydride, 3,4,4'-biphenyl sulfone tricarboxylic acid anhydride, etc. are mentioned.

<<Aromatic tetracarboxylic dianhydride>>
The aromatic tetracarboxylic dianhydride in the present invention may have any structure as long as it has two carboxylic acid anhydride groups. Specific examples include aromatic tetracarboxylic dianhydrides represented by the following general formula (30).

General formula (30)

[In general formula (30), k is 1 or 2. ]

The resin having an aromatic carboxyl group of the present invention particularly preferably has a structure represented by the general formula (2).

General formula (2)

[U1 is a hydrogen atom or a group represented by the following general formula (3),
General formula (3)

(In general formula (3), *1 represents a bond with T1, k is an integer of 1 or 2, B1 to B3 are each independently a hydrogen atom or -COOH, and B1 to B3. Of these, at least one is COOH.]
T1 is a group represented by the following general formula (4) or the following general formula (5),
General formula (4)

General formula (5)

(In the general formula (4) and the general formula (6), *2 represents a bond with U1 or U2 on the U1 side in the repeating unit, *3 represents a bond with U2 on the A3 side, P represents a monovalent polymer having a weight average molecular weight of 100 to 30,000.)

U2 is a group represented by the following general formula (7) or the following general formula (8),
General formula (7)

General formula (8)

(In the general formula (7) and the general formula (8), *4 represents a bond with T1 on the U1 side, *5 represents a bond with T1 on the A3 side in A3 or the repeating unit, (*6 represents a bond with A1, *7 represents a bond with A2, and p and r each independently represent an integer of 1 or 2.)
A1 and A2 are each independently a hydrogen atom or -COOH,
A3 is a hydroxyl group, a group represented by the following general formula (9), or a group represented by the general formula (10),
General formula (9)

General formula (10)

(In the general formulas (11) and (12), *8 represents a bond with U2, and P represents a monovalent polymer having a weight average molecular weight of 100 to 30,000.)
n is an integer of 1 to 20. ]

The weight average molecular weight of the vinyl polymer portion P of the resin represented by the general formula (2) is preferably 100 to 30,000 in order to achieve both viscosity stability and chemical resistance of the dispersion, and more preferably the weight average molecular weight. 200 to 10,000.

The weight average molecular weight of the resin represented by the general formula (2) is preferably from 1000 to 50,000 in order to achieve both viscosity stability and chemical resistance of the dispersion, and more preferably from 200 to 30,000.

When the resin represented by the general formula (2) is used as a pigment composition for a color filter, it functions as a colorant adsorbing group and a carboxyl group acting as an alkali-soluble group at the time of development, a colorant carrier and an affinity group for a solvent. The balance between the working aliphatic group and 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.

(Basic resin (B))
The basic resin (B) of the present invention is an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of a trivalent or higher polyvalent mercaptan compound (s1). It can be obtained by polymerizing (b). The basic resin (B) of the present invention has a complicated structure mainly obtained by two reactions of polymerization reaction and chain transfer reaction of ethylenically unsaturated double bond, and is represented by the general formula (structure). Since it is impossible or almost unrealistic, it will be described by the manufacturing method.

[Trivalent or higher polyvalent mercaptan compound (s1)]
The polyvalent mercaptan compound in the present invention refers to a compound having a plurality of thiol groups in one molecule. The trivalent or higher polyvalent mercaptan compound (s1) is not particularly limited as long as the number of thiol groups in one molecule is 3 or more, but from the viewpoint of the structure and molecular weight control of the basic resin (B) to be produced. Those of 3 to 10 are preferable. The number of thiol groups in one molecule may differ depending on whether it is a low molecular weight compound or a high molecular weight compound, but is usually 3 to 10, preferably 3 to 6, and more preferably 3 to 4. It can be appropriately determined within the range. Further, the trivalent or higher polyvalent mercaptan compound (s1) may be used in combination of two or more kinds.

Further, the trivalent or higher polyvalent mercaptan compound (s1) includes primary, secondary and tertiary thiols, but it is preferable to include a primary thiol from the viewpoint of improving the adhesive strength. The trivalent or higher polyvalent mercaptan compound (s1) has a molecular weight of preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less, and particularly preferably 800 or less. The lower limit of the molecular weight of the polyvalent mercaptan compound (s1) is not particularly limited, but is preferably 200 or more, more preferably 300 or more.

Examples of the polyvalent mercaptan compound (s1) include an aliphatic polythiol that may contain a hetero atom and an aromatic polythiol that may contain a hetero atom. From the viewpoint of improving the adhesive force, an aliphatic polythiol which may contain a hetero atom is preferable. Here, the "aliphatic polythiol which may contain a hetero atom" refers to an aliphatic compound which may have a hetero atom and has two or more thiol groups in one molecule. Further, the "aromatic polythiol which may contain a hetero atom" refers to an aromatic compound which may have a hetero atom and has two or more thiol groups in one molecule. From the viewpoint of improving the adhesive strength, the hetero atom preferably includes at least one selected from oxygen, nitrogen, sulfur, phosphorus, halogen and silicon, and more preferably oxygen, nitrogen, sulfur, phosphorus and halogen. It is at least one selected, and particularly preferably at least one selected from oxygen, nitrogen and sulfur.

<<Aliphatic polythiol which may contain a hetero atom>>
Examples of the aliphatic polythiol that may contain a hetero atom include, for example, a polythiol in which a moiety other than a thiol group is an aliphatic hydrocarbon, such as an alkanedithiol having 2 to 20 carbon atoms, and a halogen of a halohydrin adduct of an alcohol. Polythiol in which atoms are substituted with thiol group, polythiol comprising hydrogen sulfide reaction product of polyepoxide compound, thioglycolic acid obtained by esterification of polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and thioglycolic acid Esterification products, mercapto fatty acid esterification products obtained by esterification of polyhydric alcohols having 2 to 6 hydroxyl groups in the molecule with mercapto fatty acids, thiol isocyanurate compounds obtained by reacting isocyanurate compounds with thiols, and polysulfide groups The thiol contained, the silicone modified by the thiol group, the silsesquioxane modified by the thiol group, etc. are mentioned.

Examples of the polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule include, for example, alkanediol having 2 to 20 carbon atoms, poly(oxyalkylene)glycol, glycerol, diglycerol, trimethylolpropane, ditrimethylolpropane, Examples include pentaerythritol and dipentaerythritol. Among the examples of the aliphatic polythiol that may contain the above hetero atom, from the viewpoint of improving the adhesive strength, the polythiol in which the portion other than the thiol group is an aliphatic hydrocarbon, the halogen atom of the halohydrin adduct of alcohol is a thiol group Polythiol substituted with, polythiol consisting of hydrogen sulfide reaction products of polyepoxide compounds, thioglycolic acid esterified products, mercapto fatty acid esterified products, and thiol isocyanurate compounds are preferable, and mercapto fatty acid esterified products and thiol isocyanurate compounds are more preferable. Particularly preferred are mercapto fatty acid esterified products. From the same viewpoint, a thiol containing no polysulfide group or siloxane bond is also preferable.

(Thioglycolic acid esterified product)
Examples of the thioglycolic acid ester compound include 1,4-butanediol bisthioglycolate, 1,6-hexanediol bisthioglycolate, trimethylolpropane tristhioglycolate, and pentaerythritol tetrakisthioglycolate.

(Mercapto fatty acid ester compound)
As the mercapto fatty acid esterified product, a β-mercapto fatty acid esterified product having a primary thiol group is preferable from the viewpoint of improving the adhesive force, and β-mercaptopropionic acid of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule. Esterified products are more preferred. In addition, in the mercapto fatty acid esterified product having a primary thiol group, the number of thiol groups in one molecule is preferably 4 to 6, and preferably 4 or 5 from the viewpoint of improving the adhesive strength. It is preferably 4 and more preferably 4.

The β-mercaptopropionic acid ester compound having a primary thiol group is preferably tetraethylene glycol bis(3-mercaptopropionate) (EGMP-4), trimethylolpropane tris(3-mercaptopropionate) ( TMMP), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), and dipentaerythritol hexakis(3-mercaptopropionate) (DPMP). Among these, TMMP, PEMP and DPMP are preferable, and TMMP is more preferable.

Examples of the β-mercaptopropionic acid esterified product having a secondary thiol group include esterified products of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and β-mercaptobutanoic acid. , 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), and the like.

<<Polythiol where the part other than the thiol group is an aliphatic hydrocarbon>>
An example of the polythiol in which the portion other than the thiol group is an aliphatic hydrocarbon is an alkanedithiol having 2 to 20 carbon atoms. As the alkanedithiol having 2 to 20 carbon atoms, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,4 -Butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,10-decanedithiol, 1,1-cyclohexanedithiol, 1,2- Examples thereof include cyclohexanedithiol.

[Ethylenically unsaturated monomer (b)]
The basic resin (B) of the present invention comprises an ethylenic unsaturated monomer containing a tertiary amino group-containing ethylenically unsaturated monomer (b1) and, if necessary, other ethylenically unsaturated monomer (b2). It can be obtained by polymerizing the saturated monomer (b).
<<Ethylene unsaturated monomer having a tertiary amino group (b1)>>
The tertiary amino group in the ethylenically unsaturated monomer (b1) having a tertiary amino group is a group selected from the group consisting of a group represented by the following general formula (11) and a dialkylamino group. More preferably, it is a group represented by the following general formula (11), a group selected from the group consisting of a dimethylamino group and a diethylamino group, and even more preferably a group represented by the following general formula (11). , A diethylamino group, and most preferably a group represented by the following general formula (11).
General formula (11)

[In the general formula (11),
R ²⁰¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group, or OR ²⁰³ ,
R ²⁰³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group,
R ²⁰² independently represents an alkyl group having 1 to 8 carbon atoms, and * represents a bond. ]

In R ²⁰¹ of the general formula (11), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched, and cyclic alkyl groups, and specifically, a methyl group, an ethyl group, a normal propyl group. , Isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like. Moreover, as a C6-C20 aryl group, a phenyl group, 1-naphthyl group, 2-naphthyl group etc. can be mentioned, for example. Further, examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms, and specifically, a benzyl group and a phenethyl group. , Α-methylbenzyl group, 2-phenylpropan-2-yl group and the like. Examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group, and specific examples thereof include an acetyl group and a benzoyl group.

In the present invention, R ²⁰¹ in the general formula (11) is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an oxy radical group, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

In R ²⁰² of the general formula (11), examples of the alkyl group having 1 to 8 carbon atoms include linear, branched, and cyclic alkyl groups, and specifically, a methyl group, an ethyl group, a normal propyl group. , Isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like. An alkyl group having 1 to 3 carbon atoms is preferable.

Specific examples of the ethylenically unsaturated monomer (b1) having a tertiary amino group represented by the general formula (11) include compounds represented by the following general formulas (a-1) to (a-11). I can name it. ^{R 204} in the formula (a-1) ~ (a -11) represents a hydrogen atom or a methyl group

Among these, the monomers represented by (a-1), (a-2), (a-8), and (a-9) are preferable, and represented by (a-1) and (a-2). Monomers are more preferred.

<Colorant>
The photosensitive coloring composition of the present invention contains a coloring agent such as an organic pigment, an inorganic pigment, an organic dye or an inorganic dye. These may be used alone or in any combination of two or more. It is preferable to use an organic pigment in the color filter coloring composition of the present invention, for example, azo pigments, azo metal complex pigments, phthalocyanine pigments, azomethine pigments, quinacridone pigments, isoindolinone pigments, Isoindoline pigments, quinophthalone pigments, perylene pigments, perinone pigments, dioxazine pigments, triarylmethane pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansanthuron pigments, indance pigments Examples thereof include ron-based pigments, flavanthuron-based pigments, pyranthrone-based pigments, squarylium-based pigments, diketopyrrolopyrrole-based pigments and the like.
Typical pigments and dyes that can be used in the present invention are listed below.

Red pigments that can be used in the present invention include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48: 4, 49, 49:1, 49:2, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, or the diketopyrrolopyrrole pigment described in JP-A No. 2011-523433, but the invention is not particularly limited thereto. Further, red dyes such as xanthene type, azo type, disazo type, anthraquinone type and dipyrromethene type can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, 338.

Orange pigments that can be used in the present invention include, for example, C.I. I. Pigment Orange 38, 43, 71, 73 or the like, but is not particularly limited thereto.

Yellow pigments that can be used in the present invention include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or the quinophthalone pigments described in Japanese Patent No. 4993026, and the like, but especially these Not limited to. Further, yellow dyes such as quinoline type, azo type, methine type, coumarin type and isoindoline type dyes can also be used.

Green pigments that can be used in the present invention include, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, JP 2008-19383A, JP 2007-320986A, JP 2004-70342A, JP 2016-57635A, and WO 2015/118720. Examples include zinc phthalocyanine pigments described in Japanese Patent Publication No. Pamphlet, aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, JP-A-2016-153481, etc., but are not particularly limited thereto. Further, blue-green dyes such as triarylmethane type, phthalocyanine type and squarylium type can also be used.

Blue pigments that can be used in the present invention include, for example, C.I. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, JP-A-2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859 and the like, but are not particularly limited thereto.

Purple pigments that can be used in the present invention include, for example, C.I. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Examples thereof include, but are not limited to, 37, 39, 42, 44, 47, 49 and 50.

The coloring composition for a color filter of the present invention includes titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, metal oxides such as silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, and yellow lead. Inorganic pigments such as carbon black can also be used.

As the coloring agent used in the coloring composition of the present invention, a halogenated phthalocyanine pigment is preferable from the viewpoint of excellent brightness and contrast of green pixels. Examples of the halogenated phthalocyanine pigment include C.I. I. Pigment Green 7, 36, 58, and those described in JP-A-2016-57635 and JP-A-2016-153481. Among them, the central metal is preferably zinc or aluminum from the viewpoint of brightness, and further, a halogenated aluminum phthalocyanine pigment represented by the following general formula (100) and C.I. I. Pigment Green 58 is more preferably one selected from the group consisting of Pigment Green 58. The basic resin (B) having a specific structure, which will be described in detail later, effectively works to disperse the aluminum phthalocyanine pigment and maximizes the performance of the aluminum phthalocyanine pigment.

General formula (100)

[In general formula (100), X represents a halogen atom, and n represents an integer of 2 to 16. However, the average value of the number of substitutions of the halogen atom represented by X is 4 to 15, and the halogen distribution width is 4 or more. Y ^{represents -OP (= O) R 101 R} 102, -OC (= O) R 103, -OS (= O) 2 R 104. R ¹⁰¹ and R ¹⁰² are each independently a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent, or a substituent. Represents an aryloxy group which may have a group. R ¹⁰³ is a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an aryl group which may have a substituent or a hetero group which may have a substituent. Represents a ring group. R ¹⁰⁴ represents a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ]

Each substituent in the general formula (100) will be described below.
Examples of the halogen include fluorine, bromine, chlorine and iodine, and two or more kinds may be used in combination. Bromine and chlorine are preferable, and bromine (Br) is particularly preferable from the viewpoint of brightness.

The alkyl group for R ^{101 to} R ¹⁰⁴ is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group. , A linear or branched alkyl group such as a 2-ethylhexyl group, and an alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group such as a methoxy group, an aryl group such as a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the alkyl group having a substituent include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and a 2-butoxy group. Examples thereof include an ethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group.

Examples of the aryl group for R ^{101 to} R ¹⁰⁴ include a monocyclic aromatic hydrocarbon group such as a phenyl group and a p-tolyl group, and a condensed aromatic hydrocarbon group such as a naphthyl group and an anthryl group. Hydrocarbon groups are preferred. Further, an aryl group having 6 to 12 carbon atoms is preferable. Examples of the substituent of the aryl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the aryl group having a substituent include a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-dimethylaminophenyl group, Examples thereof include a 2-methyl-4-chlorophenyl group, a 4-methoxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group and an anthraquinonyl group.

As the alkoxyl group for R ¹⁰¹ and R ¹⁰² , a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, 2,3-dimethyl-3- Examples thereof include linear or branched alkoxyl groups such as a pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group, and an alkoxyl group having 1 to 6 carbon atoms is preferable. Examples of the substituent of the alkoxyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkoxyl group, an aryl group such as a phenyl group and a tolyl group, and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the alkoxyl group having a substituent include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, and a 2,2- Examples thereof include a ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group and a benzyloxy group.

The aryloxy group in R ¹⁰¹ and R ¹⁰² is an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group or a p-methylphenoxy group, or a condensed aromatic hydrocarbon such as a naphthaloxy group or an anthryloxy group. The aryloxy group consisting of a group is mentioned, and the aryloxy group consisting of a monocyclic aromatic hydrocarbon group is preferable. Further, an aryloxy group having 6 to 12 carbon atoms is preferable. Examples of the substituent of the aryloxy group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Therefore, examples of the aryloxy group having a substituent include a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group. Can be mentioned.

Examples of the cycloalkyl group in R ¹⁰³ include a monocyclic aliphatic hydrocarbon group such as a cyclopentyl group, a cyclohexyl group, a 2,5-dimethylcyclopentyl group, and a 4-tert-putylcyclohexyl group, and a bornyl group and an adamantyl group. Examples include condensed aliphatic hydrocarbon groups. Further, a cycloalkyl group having 5 to 12 carbon atoms is preferable. Examples of the substituent of the cycloalkyl group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Examples of the cycloalkyl group having a substituent include a 2,5-dichlorocyclopentyl group and a 4-hydroxycyclohexyl group.

Examples of the heterocyclic group for R ¹⁰³ and R ¹⁰⁴ include an aliphatic heterocyclic group such as a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, and an acridinyl group, and an aromatic heterocyclic group. Further, a heterocyclic group having 4 to 12 carbon atoms is preferable, and a heterocyclic group having 5 to 13 ring members is preferable. Examples of the substituent of the heterocyclic group having a substituent include a halogen atom such as chlorine, fluorine and bromine, an alkyl group, an alkoxyl group, a hydroxyl group, an amino group and a nitro group. Further, there may be a plurality of substituents. Examples of the heterocyclic group having a substituent include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group and the like.

In the aluminum phthalocyanine pigment represented by the general formula (100), from the viewpoint of dispersibility and color characteristics, at least one of R ¹⁰¹ and R ¹⁰² has an aryl group or a substituent which may have a substituent. It is preferably an aryloxy group which may have, more preferably both R ¹⁰¹ and R ¹⁰² are an aryl group or an aryloxy group, and both R ¹⁰¹ and R ¹⁰² are a phenyl group or a phenoxy group. It is more preferable that there is. Further, R ¹⁰³ and R ¹⁰⁴ are preferably an aryl group which may have a substituent or a heterocyclic group which may have a substituent. More preferably, Y is —OP(═O)R ¹⁰¹ R ¹⁰² .

In the aluminum phthalocyanine pigment represented by the general formula (100), the average value of the substitution number of the halogen atom represented by X is 4 to 15, and 8 to 15 is preferable from the viewpoint of hue and fastness. The halogen distribution width is 4 or more, preferably 4 to 9. When the halogen distribution width is 4 or more, the association between the phthalocyanine molecules is apt to be significantly suppressed, and it is clear that the particle size is increased due to the association between the molecules and, as a result, the reduction of the contrast is greatly suppressed. became. Here, the "halogen distribution width" is a distribution of the number of halogens substituted in the aluminum phthalocyanine pigment represented by the general formula (100). The halogen distribution width, in the mass spectrum obtained by mass spectrometry, the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value obtained by integrating each peak value (total peak value), The number of peaks in which the ratio of each peak value to the total peak value was 1% or more was counted and used as the halogen distribution width.

In the present invention, the aluminum phthalocyanine pigment represented by the general formula (100) is represented by [AlPc(Y)]Xn (2≦n≦16) (where Pc is a phthalocyanine ring, X is a halogen atom, and n is 2 to 2). 16 is represented by each), as a typical example of the general formula (100), [AlPc(Y)]Brn(2≦n≦16), [AlPc(Y)]Cln(2≦ n≦16), [AlPc(Y)]In (2≦n≦16), [AlPc(Y)]Fn (2≦n≦16) and the like, but the present invention is not limited thereto. is not. In addition, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

Typical examples of Y in the general formula (100) include the structures shown below (* represents the bonding position of the substituent with Al in the general formula (100)), but the present invention is not limited to these. It is not limited to. In addition, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

<Refinement of pigment>
When the coloring agent used in the coloring composition for a color filter of the present invention is a pigment, it is preferable to use it in a finer size from the viewpoint of contrast. The micronization method is not particularly limited, and for example, any of wet milling, dry milling, and dissolution precipitation method can be used. As illustrated in the present invention, salt milling treatment by a kneader method, which is one type of wet milling. It is possible to miniaturize by performing the above. The average primary particle diameter of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, it may not be possible to obtain a sufficient contrast ratio. For this reason, the more preferable average primary particle diameter is in the range of 10 to 70 nm.

The salt milling treatment is a batch type or continuous type of a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent, such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill and a planetary mixer. This is a treatment of mechanically kneading while heating with a kneader, and then washing with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution range, and a sharp particle size distribution.

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

The water-soluble organic solvent has a function of wetting the pigment and the 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 used. However, a high boiling point solvent having a boiling point of 120° C. or higher is preferable from the viewpoint of safety, because the temperature rises during salt milling and the solvent is easily evaporated. 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 and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the salt is subjected to the salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and natural resin, modified natural resin, synthetic resin, synthetic resin modified with natural resin, and the like can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Dye derivative>
The coloring composition for a color filter of the present invention can optionally contain various conventionally known dye derivatives. Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone, or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent. 63-305173, JP-B 57-15620, JP-B 59-40172, JP-B 63-17102, JP-B-5-9469, JP 2001-335717, JP 2003-2003. 128669, JP2003-167112A, JP2004-091497A, JP2004-307854A, JP2007-156395A, JP2008-094873A, and JP2008-094986A. The materials described in Japanese Patent Laid-Open No. 2008-095007, Japanese Patent Laid-Open No. 2008-195916, Japanese Patent No. 4585781 and the like can be used, but are not limited thereto. The dye derivative may be added at the time of pigmentation such as salt milling treatment, or may be added at the time of dispersion.

<Binder resin>
The binder resin used in the coloring composition of the present invention disperses, dyes, or permeates a colorant, and examples thereof include a thermoplastic resin. When used in the form of an alkali development type colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, an active energy ray-curable resin having an ethylenically unsaturated double bond can be used to further improve the photosensitivity.

In particular, when an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain is used for an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the colorant is fixed, heat resistance is improved, and discoloration (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. Further, it also has an effect of suppressing aggregation/precipitation of the colorant component even in the developing step.

The binder resin is preferably a resin having a spectral transmittance of 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 2,000 to 100,000, more preferably in the range of 3,000 to 20,000, in order to disperse the colorant preferably, and Mw/ The value of Mn is preferably 10 or less.

When using a binder resin as a photosensitive coloring composition for a color filter, a carboxyl group that acts as a colorant adsorbing group and 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 aromatic groups 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 a developing solution is poor and it may be difficult to form a fine pattern. If it exceeds 300 mgKOH/g, fine patterns may not remain.

Since the binder resin has good film-forming properties and various resistances, it is preferable to use the binder resin in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant, which has a high colorant concentration and good color characteristics. 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. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and 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 thereof include isobutylene/(anhydrous) maleic acid copolymer. Above all, 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 it has 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 methods (i) and (ii) shown below.

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

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, And 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more kinds. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth)acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted compounds. Examples thereof include monocarboxylic acid, and these may be used alone or in combination of two or more kinds.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. These may be used alone or in combination of two or more kinds. I don't care. If necessary, such as increasing the number of carboxyl groups, use a tricarboxylic acid anhydride such as trimellitic anhydride, or use a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to leave the remaining anhydride. It is also possible to hydrolyze the group. Further, when the polyethylenic acid anhydride is etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond, the unsaturated ethylenic double bond can be further 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 of adding an unsaturated ethylenic monomer having an epoxy group to a part of the 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 an unsaturated monobasic acid monomer having another carboxyl group is copolymerized with another monomer. There is a method of reacting a side chain hydroxyl group of the obtained copolymer with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

As the unsaturated ethylenic monomer having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol Examples thereof include (meth)acrylates and hydroxyalkyl (meth)acrylates such as cyclohexanedimethanol mono(meth)acrylate, and these may be used alone or in combination of two or more kinds. Further, a polyether mono(meth)acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and/or butylene oxide to the hydroxyalkyl(meth)acrylate, (poly)γ-valerolactone, (poly)ε-caprolactone And/or a (poly)ester mono(meth)acrylate to which (poly)12-hydroxystearic acid or the like is added can also be used. From the viewpoint of suppressing foreign matter in 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 and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but the invention is not limited thereto. Alternatively, two or more types can be used together.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is the binder resin. Examples of thermosetting compounds include epoxy compounds and/or resins, oxetane compounds and/or resins, benzoguanamine compounds and/or resins, rosin-modified maleic acid compounds and/or resins, rosin-modified fumaric acid compounds and/or resins, Examples include melamine compounds and/or resins, urea compounds and/or resins, phenol compounds and/or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, a coloring agent is sufficiently dispersed and permeated in a coloring agent carrier and coated on a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a colored film. It contains an organic solvent to facilitate its formation. The organic solvent is selected in consideration of good coatability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 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, N,N-dimethyl. Acetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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 monotert-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 mono Methyl 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 propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Propyl acetate, dibasic acid esters and the like.
These solvents may be used singly or as a mixture of two or more kinds at an arbitrary ratio as needed.

Among them, dispersibility of the colorant, penetrability, and good coatability of the coloring composition, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol, diacetone alcohol and 3-methoxybutanol, and ketones such as cyclohexanone.

The organic solvent is used in an amount of 500 to 4000 parts by weight, relative to 100 parts by weight of the colorant, since the organic solvent can adjust the viscosity of the coloring composition to an appropriate level and form a colored film having a desired uniform thickness. Is preferred.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or oligomer that is cured by ultraviolet rays or heat to form a transparent resin.

Examples of the monomer or oligomer that is 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 diglycidyl ether 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, tricyclodecanyl (meth)acrylate, ester acrylate, methylolated melamine Various (meth)acrylic acid esters, epoxy (meth)acrylates, urethane acrylates and other acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol triester Examples thereof include, but are not limited to, vinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.
These photopolymerizable compounds may be used alone or in combination of two or more at an arbitrary ratio as needed.

The compounding amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
The coloring composition of the present invention is a solvent-developable or alkali-development type photosensitive coloring composition in which a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method. Can be prepared in the form of

As the photopolymerization initiator, 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 Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′. -Methyldiphenyl sulfide, or benzophenone-based compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as diisopropylthioxanthone or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-( p-methoxyphenyl)-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- Triazine compounds such as trichloromethyl-(4′-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl) Oxime)], or oxime ester compounds such as O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; bis(2,4,6) -Trimethylbenzoyl)phenylphosphine oxide, or a phosphine compound such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; a quinone compound such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; a borate compound; A carbazole compound; an imidazole compound; or a titanocene compound is used.
These photopolymerization initiators can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer.
Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, etc., 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives. , Polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonole derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, biimidazole derivative, α -Acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3', or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned. These sensitizers can be used alone or in a mixture of two or more kinds at an arbitrary ratio if necessary.

More specifically, Nobu Okawara et al., "Dye Handbook" (1986, Kodansha), Nobu Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), Tadaburo Ikemori et al. Examples of the sensitizer include those described in "Special Function Material" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near-infrared region may be contained.

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 coloring composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Multifunctional thiol>
The coloring composition of the present invention may contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, and ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionate tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-Trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like can be mentioned. These polyfunctional thiols can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the weight (100% by weight) of the total solid content of the color filter coloring composition. .. When the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient.

<Antioxidant>
The coloring composition of the present invention may contain an antioxidant. The antioxidant enhances the transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition from being oxidized and yellowing due to the thermal process during thermosetting or ITO annealing. be able to. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented and a high transmittance of the coating film can be obtained.

The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function, and specifically, as a antioxidant, a hindered phenol type, a hindered amine type. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants and the like can be used.

Among these antioxidants, from the viewpoint of compatibility of the transmittance and the sensitivity of the coating film, preferred are hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants or sulfur antioxidants. Agents. Further, more preferably, it is a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant.

These antioxidants can be used singly or as a mixture of two or more kinds at an arbitrary ratio according to need.

The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the coloring composition for a color filter (100% by weight) because the brightness and sensitivity are good.

<Amine compound>
In addition, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine and the like can be mentioned.

<Leveling agent>
A leveling agent is preferably added to the colored composition of the present invention in order to improve the leveling property of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its 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 BYK 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 together. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight, based on the total weight of the coloring composition (100% by weight).

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a small hydrophilicity even though having a hydrophilic group, when added to the coloring composition, It has the characteristic of low surface tension lowering ability, and it is useful that it has good wettability to the glass plate in spite of the low surface tension lowering ability. Those that can sufficiently suppress the charging property can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxane may have both polyethylene oxide units and polypropylene oxide units.

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. It may be of a linear block copolymer type in which alternately and repeatedly bonded. 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. -207, but not limited thereto.

Anionic, cationic, nonionic or amphoteric surfactants can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used. Examples of anionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, and alkyldiphenyletherdisulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples thereof include esters.

Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants that are supplementarily added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate. Examples thereof include polyethylene glycol monolaurate and the like; alkylbetaine such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based or silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, etc., if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and thermosetting resins Any curing agent may be used as long as it can react with. Among these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferable. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl). -N,N-dimethylbenzylamine etc.), quaternary ammonium salt compound (eg triethylbenzylammonium chloride etc.), blocked isocyanate compound (eg dimethylamine etc.), imidazole derivative bicyclic amidine compound and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2- Ethyl-4-methylimidazole etc.), phosphorus compounds (eg triphenylphosphine etc.), guanamine compounds (eg melamine, guanamine, acetoguanamine, benzoguanamine etc.), S-triazine derivatives (eg 2,4-diamino-6). -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine/isocyanuric acid adduct, 2,4-diamino-6- Methacryloyloxyethyl-S-triazine/isocyanuric acid adduct) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent may be contained in order to improve the adhesion to the transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the colorant.

Examples of the adhesion improver 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-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(amino Ethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples of the silane coupling agent include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention contains a colorant in a colorant carrier such as a dispersant or a binder resin and/or a solvent, preferably together with a dispersion aid (a dye derivative or a surfactant), and a kneader, two lines. It can be finely dispersed and manufactured using various dispersing means such as a 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 and the like may be dispersed in the colorant carrier at the same time, or those separately dispersed in the colorant carrier may be mixed. When the colorant such as a dye has a high solubility, specifically, it has a high solubility in the solvent used and is dissolved by stirring, and if no foreign matter is confirmed, it is produced by finely dispersing it as described above. No need.

When used as a photosensitive coloring composition for a color filter (resist material), it can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent-developable or alkali-developable coloring composition comprises the colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and, if necessary, a solvent, another dispersion aid, and an additive. 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.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a dispersant and a surfactant can be appropriately contained. Since the dispersion aid has a large effect of preventing the re-aggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness, contrast and storage stability. Good quality. The dye derivative and the dispersant are as described above.

<Surfactant>
As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate. Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, styrene-acrylic acid copolymer monoethanolamine, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkylbetaine such as alkyldimethylaminoacetic acid betaine and alkylimidazoline, and these may be used alone or in combination of two or more. Although they can be used as a mixture, they are not necessarily limited thereto.

When a surfactant is added, it is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant. If the content of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by weight, the dispersion may be affected by the excess dispersant. ..

<Removal of coarse particles>
The colored composition of the present invention has a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, and more preferably a coarse particle of 0.5 μm or more, by means of centrifugation, filtration with a sintering filter or a membrane filter, and the like. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. It is more preferably 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 comprises a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment. In the color filter of the present invention, at least one of a red filter segment, a green filter segment and a yellow filter segment is formed from the pigment composition of the present invention. In particular, it is preferable that the green filter segment is formed from the pigment composition of the present invention.

<Method of manufacturing color filter>
The color filter can be manufactured by a printing method or a photolithography method. Since the formation of the filter segment by the printing method can be patterned by simply printing and drying the coloring composition prepared as the printing ink, the manufacturing method of the color filter is low cost and excellent in mass productivity. Furthermore, the development of printing technology enables printing of fine patterns having high dimensional accuracy and smoothness. For printing, it is preferable that the composition is such that the ink does not dry and solidify on the printing plate or on the blanket. In addition, it is important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developing or alkali-developing colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. Depending on the method, it is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern which is provided in contact with or not in contact with the film. After that, after immersing in a solvent or an alkaline developer or spraying a developer with a spray 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 carried out if necessary. According to the photolithography method, it is possible to manufacture a color filter with higher accuracy than the above printing method.

Upon development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
In order to increase the exposure sensitivity, after coating and drying the above-mentioned colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is coated and dried to form a film for preventing polymerization inhibition by oxygen. Exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by utilizing a transparent conductive film formed on a substrate to form each color filter segment on the transparent conductive film by electrophoretic deposition 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 the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before forming each color filter segment on the transparent substrate or the reflective substrate. 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, but the black matrix is not limited thereto. Further, it is also possible to previously form a thin film transistor (TFT) on the transparent substrate or the reflective substrate, and then form each color filter segment. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as needed.

The color filter of the present invention is laminated with a counter substrate using a sealant, and after injecting a liquid crystal from an injection port provided in the sealing portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is provided on the substrate. A color liquid crystal display device is manufactured by laminating the color liquid crystal display device on the outside. This color liquid crystal display device includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Alignment (VA), Opticly Convenient Bend (OCB). ) And the like can be used in a liquid crystal display mode in which colorization is performed using a color filter.

Further, the color filter of the present invention can be used for manufacturing a color image pickup device, an organic EL display device, an electronic paper, etc. other than the color liquid crystal display device.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “parts” and “%” represent “parts by mass” and “mass %”. Moreover, Mn and Mw mean a number average molecular weight and a weight average molecular weight, respectively.

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

(Average Molecular Weight of Binder Resin and Dispersant (A) Having Aromatic Carboxyl Group)
The weight average molecular weight (Mn) and number average molecular weight (Mw) of the acrylic resin used as the binder resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as a device, two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was used in a double connection for both packing materials, with an oven temperature of 40. The temperature was measured at a temperature of 0.35 ml/min using a THF solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in an amount of 20 microliters. All molecular weights are polystyrene equivalent values.

(Acid Value of Binder Resin and Dispersant (A) Having Aromatic Carboxyl Group)
The resin acid value is a value obtained by converting the measured acid value (mgKOH/g) into solid content in accordance with the potentiometric titration method of JIS K0070.

(Average molecular weight of basic resin (B))
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the basic resin type dispersant are HLC-8320GPC (manufactured by Tosoh Corporation) as a device, SUPER-AW3000 as a column, and 30 mM triethylamine as an eluent. And a polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using a 10 mM LiBr N,N-dimethylformamide solution.

(Amine value of basic resin (B))
The amine value of the basic resin type dispersant is a value obtained by converting the total amine value (mgKOH/g) measured in terms of solid content according to the method of ASTM D 2074.

(Halogen distribution width)
The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (autoflex III (TOF-MS), manufactured by Bruker Daltonics). In the mass spectrum obtained by mass spectrometric analysis of the pigment powder, the halogen content is the signal intensity of each molecular ion peak corresponding to each component (each peak value) and the value obtained by integrating each peak value (all peak values). Was calculated and calculated from the ratio of each peak value to the total peak value. The halogen distribution width was defined as the halogen distribution width by counting the number of peaks in which the ratio of each peak value to all peak values was 1% or more.

Subsequently, the pigments, dye derivatives, binder resin solutions, dispersants (A) having an aromatic carboxyl group, basic resins (B), coloring compositions for color filters, and photosensitive coloring compositions used in Examples and Comparative Examples. A method for manufacturing a product will be described.

<Method for producing pigment and dye derivative>
(Production of halogenated zinc phthalocyanine pigment (PG-1))
C. I. Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 100 parts, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating at 70° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a whole day and night. A zinc phthalocyanine pigment (PG-1) was obtained. The average primary particle diameter was 32.5 nm.

(Production of halogenated aluminum phthalocyanine pigment (PG-2))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (200), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, The reaction was carried out at 20° C. for 4 hours. Then, the above reaction mixture was poured into 5000 parts of 3° C. ice water, and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added, and the mixture was stirred at 80° C. for 1 hour. Then, this mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 8.0 bromine atoms substituted on the obtained phthalocyanine ring and 15.8 parts of diphenyl phosphate were added to a three-necked flask, and 90 parts The mixture was heated to ℃ and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a phthalocyanine pigment (PG-2) represented by the following formula (201). The halogen distribution width was 9.

Formula (200)

Formula (201)

(Production of quinophthalone pigment (PY-1))
100 parts of PY138 (BASF Corporation Pariotor Yellow K0961HD), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 65° C. for 8 hours. This kneaded product was poured into 3000 parts of warm water and stirred at 70° C. for 1 hour to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a whole day and night to give quinophthalone. A pigment (PY-1) was obtained. The average primary particle diameter was 29.0 nm.

(Production of Dye Derivative (H-1))
A dye derivative (H-1) was obtained according to the synthesis method of JP-A-2004-067715.
Dye derivative (H-1)

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, and heated to 120° C. while injecting nitrogen gas into the vessel. At the temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 25.0 parts of dicyclopentanyl methacrylate, 16 parts of methyl methacrylate and azobisisobutyro as a catalyst required for the reaction of the precursor at this stage A mixture of 1.0 part of nitrile was added dropwise over 2.5 hours to carry out a polymerization reaction. Then, the inside of the flask was replaced with air, and 17.0 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone as a catalyst required for the reaction of the precursor in this stage were charged, and the mixture was heated at 120° C. The reaction was carried out for 5 hours to obtain a resin solution having a weight average molecular weight of about 12000 (measured by GPC). The added acrylic acid does not form a carboxyl group in the resin structure because it forms an ester bond with the epoxy group terminal of the glycidyl methacrylate constituent unit. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor in this stage were added and reacted at 120° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups formed by cleavage of the carboxylic acid anhydride site forms an ester bond with the hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. Acrylic resin solution 1 was obtained by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 40%.

<Production of Aromatic Carboxyl Group-Containing Resin (A)>
(Production of Aromatic Carboxyl Group-Containing Resin (A-1))
50 parts of methyl methacrylate, 45 parts of t-butyl acrylate, 5.0 parts of methacrylic acid, 2.0 parts of 3-mercapto-1,2-propanediol were placed in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer. 0.1 part of 2'-azobisisobutyronitrile and 102 parts of PGMAc were added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Subsequently, 3.2 parts of pyromellitic dianhydride, 6.0 parts of PGMAc, and 0.20 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 7 hours. Let The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain Dispersant Solution A-1 having an acid value of 46.7 and a weight average molecular weight of 19,500.

(Production of Aromatic Carboxyl Group-Containing Resin (A-2))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 30 parts of methyl methacrylate, 30 parts of t-butyl acrylate, 35 parts of ethyl acrylate, 5.0 parts of methacrylic acid, 3-mercapto-1,2-propane. 2.0 parts of diol, 0.1 part of 2'-azobisisobutyronitrile, and 102 parts of PGMAc were added and reacted for 10 hours. Solid content measurement confirmed that 95% had reacted. Subsequently, 6.0 parts of trimellitic anhydride, 6.0 parts of PGMAc, and 0.20 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 7 hours. Let The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain Dispersant Solution A-2 having an acid value of 66.5 and a weight average molecular weight of 9,500.

<Method for producing basic resin (B)>
(Production Example of Basic Resin (B-1))
80 parts of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 7 parts of methyl methacrylate, 8 parts of 2-hydroxyethyl methacrylate, benzyl were placed in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer. 5 parts of acrylate, trimethylolpropane tris(3-mercaptopropionate); 4.0 parts of TMMP, 0.1 part of 2,2′-azobis(2,4-dimethylvaleronitrile), 104 parts of PGMAc were added, and 90 parts were added. The reaction was carried out at 0°C for 10 hours. Solid content measurement confirmed that 95% had reacted. Thus, a basic resin (B-1) having a solid content of 50%, an amine value per solid content of 185 mgKOH/g, and a weight average molecular weight (Mw) of 10,100 was obtained.

(Production Example of Basic Resins (B-2)-(B-10))
A basic resin solution (B) was synthesized in the same manner as the basic resin (B-1) except that the raw materials were changed as shown in Table 1, and the basic resin (B-2)-(B-10). A solution was obtained.

(Production Example of Basic Resin (B-11) Without Using Polyvalent Mercaptan Compound)
50 parts of methoxypropyl acetate was charged into a reaction tank equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and the temperature was raised to 110° C. while substituting with nitrogen. In a dropping tank, 80 parts of dimethylaminoethyl methacrylate, 7 parts of methyl methacrylate, 5 parts of 2-hydroxyethyl methacrylate, 8 parts of benzyl acrylate, 54 parts of methoxypropyl acetate, and 2,2′-azobis(2,4-dimethylvaleronitrile). Was charged into the reaction tank over 2 hours, and then the reaction was continued at the same temperature for 3 hours. Thus, a basic resin (B-11) having a solid content of 50%, an amine value per solid content of 270 mgKOH/g, and a weight average molecular weight of 10,400 (Mn) and having no polyvalent mercaptan compound was obtained.

(Production Example of Basic Resin (B-12)-(B-13))
A basic resin solution (B) was synthesized in the same manner as the basic resin (B-11) except that the raw materials were changed as shown in Table 1, and the basic resin (B-12)-(B-13) A solution was obtained.

The abbreviations in Table 1 are shown below.
TMMP: trimethylolpropane tris (3-mercaptopropionate)
TEMPIC: tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate PEMP: pentaerythritol tetrakis (3-mercaptopropionate)
DPMP: dipentaerythritol hexakis (3-mercaptopropionate)
DMAEMA: dimethylaminoethyl methacrylate DEAEMA: diethylaminoethyl methacrylate LA-82: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate DMAPAA: dimethylaminopropyl acrylamide MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate BzA: Benzyl methacrylate

<Method for producing colored composition for color filter>
(Production Example of Coloring Composition (CP-1))
After stirring and mixing the mixture having the following composition so as to be uniform, the mixture was dispersed for 5 hours by an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using 0.5 mm diameter zirconia beads, and then 5 It filtered with a 0.0-micrometer filter and produced the coloring composition (CP-1).
Aluminum halide phthalocyanine pigment (PG-2): 12.0 parts Aromatic carboxyl group-containing resin solution (A-2): 6.0 parts Basic resin solution (B-1): 3.0 parts Acrylic resin solution 1 :11.0 parts Propylene glycol monomethyl ether acetate: 68.0 parts

(Production Example of Coloring Composition (CP-2 to 16))
Coloring compositions (CP-2 to 16) were obtained in the same manner as the coloring composition (CP-1) except that the types of the coloring agent and the resin were changed as shown in Table 2.

<Evaluation of coloring composition>
The contrast and storage stability of the obtained colored compositions (CP-1 to 16) were evaluated by the following methods. Table 2 shows the evaluation results.

(Evaluation of contrast)
The coloring composition (CP-1 to 16) was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater and changing the rotation speed so that the film thickness of 1.5 μm would be the center value. Three levels of coated substrates were prepared. Drying conditions were 70° C./20 minutes after coating and further 230° C./30 minutes. Further, the film thickness of the coating film was measured by using Dektak 3030 (manufactured by Nippon Vacuum Engineering Co., Ltd.), and the contrast at the film thickness of 1.5 μm was determined by the linear correlation method from the data of 3 points. The contrast was evaluated according to the following 5 grades.
5:6000 or more 4:5000 or more, less than 6000 3:4000 or more, less than 5000 2:3000 or more, less than 4000 1:less than 3000

(Storage stability)
The initial viscosity at 25° C. of the obtained coloring composition was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.). Then, after being stored in a thermostat at 40° C. for 2 weeks to accelerate the aging, the viscosity after aging is measured by the same method as the above-mentioned viscosity measurement, and the change rate of the viscosity before and after the storage at 40° C. for 2 weeks is calculated. However, the following criteria evaluated it in three steps.
5: Viscosity change rate of ±5% or less 4: Viscosity change rate of +5% to +10%, or -5% to -10% range 3: Viscosity change rate of +10% to +15%, or- In the range of 10% to -15% 2: When the rate of change in viscosity is +15% to +20%, or in the range of -15% to -20% 1: When the rate of change in viscosity exceeds ±20%

The abbreviations in Table 2 are shown below.
BYK6919: BYK-LPN6919 manufactured by Big Chemie

<Method for producing photosensitive coloring composition>
(Coloring composition (CY-1): PY138 coloring composition)
After stirring and mixing the mixture having the following composition so as to be uniform, the mixture was dispersed for 5 hours by an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using 0.5 mm diameter zirconia beads, and then 5 A colored composition (CY-1) was produced by filtering with a filter of 0.0 μm.
Quinophthalone pigment (PY-1): 10.8 parts Dye derivative (H-1): 1.2 parts Resin type dispersant solution (BYK-LPN6919 manufactured by BYK Chemie): 4.0 parts Acrylic resin solution 1: 14.0 Part Propylene glycol monomethyl ether acetate: 70.0 parts

[Example 1]
(Production of Photosensitive Coloring Composition (CR-1))
The mixture having the following composition was uniformly stirred and mixed, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (CR-1).
Coloring composition (CP-1): 20.0 parts Coloring composition (CY-1): PY138 Coloring composition: 18.5 parts Acrylic resin solution 1: 10.5 parts Photopolymerizable monomer (Toagosei Co., Ltd. "Aronix M402"): 2.6 parts Photopolymerizable monomer ("Aronix M350" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("IRGACURE OXE02" manufactured by BASF): 1.2 Part Propylene glycol monomethyl ether acetate: 42.2 parts Propylene glycol monomethyl ether: 3.0 parts

[Examples 2 to 10, 12 and Comparative Examples 1 to 4]
(Production of Photosensitive Coloring Compositions (CR-2 to 16))
Photosensitive coloring compositions (CR-2 to 16) were obtained in the same manner as the photosensitive coloring composition (CR-1) except that the kind of the coloring composition was changed as shown in Table 3.

[Example 11]
(Production of Photosensitive Coloring Composition (CR-11))
The mixture having the following composition was uniformly stirred and mixed, and then filtered with a 1.0 μm filter to obtain a green photosensitive coloring composition (CR-11).
Coloring composition (CP-11): 28.5 parts Coloring composition (CY-1): PY138 Coloring composition: 10.0 parts Acrylic resin solution 1: 10.5 parts Photopolymerizable monomer (Toagosei Co., Ltd. "Aronix M402" manufactured by: 2.6 parts Photopolymerizable monomer ("Aronix M350" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("Irgacure OXE02" manufactured by BASF): 1.2 Part Propylene glycol monomethyl ether acetate: 42.2 parts Propylene glycol monomethyl ether: 3.0 parts

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring composition was evaluated by the following methods. The results are shown in Table 3.
(Evaluation of brightness)
The photosensitive coloring composition (CR-1 to 16) was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by using a spin coater and heated in a clean oven at 70° C. for 15 minutes to remove the solvent. A coating film was obtained by removing. Subsequently, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed at an integrated light amount of 200 mJ/cm ² , and development was performed with an alkali developing solution at 23° C. to obtain a coated substrate. Then, after heating in a clean oven at 230° C. for 30 minutes and allowing to cool, the brightness Y(C) of the obtained coated substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The green coating substrate was heat-treated at 230° C. and then adjusted to a chromaticity of (x=0.270, y=0.580) with a C light source. The alkaline developer is composed of sodium carbonate 1.5% by mass, sodium hydrogencarbonate 0.5% by mass, an anionic surfactant (Pelex Rex NBL manufactured by Kao Corporation) 8.0% by mass and water 90% by mass. Was used. The lightness was evaluated according to the following 5 grades.
5: 61.0 or more 4: 60.0 or more, less than 61.0 3: 59.0 or more, less than 60.0 2: 58.0 or more, less than 59.0 1: less than 58.0

(Adhesion evaluation)
The photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm×100 mm and a thickness of 1.1 mm by a spin coater at a rotation speed such that the film thickness after drying was 2 μm, and the substrate was dried at 70° C. for 20 minutes. Ultraviolet rays of 150 mJ/cm 2 were irradiated using an ultra-high pressure mercury lamp through a photomask having 100 openings of 10 μm×10 μm. Next, after undeveloped portions were removed by spray development with an alkaline developer containing 0.2 wt% sodium carbonate aqueous solution, washing was performed with ion-exchanged water. At this time, the adhesiveness was evaluated based on how many 10 μm×10 μm patterns remained. The developability was evaluated according to the following criteria.
5: 90 or more patterns remaining 4: 80 to 89 patterns remaining 3: 70 to 79 patterns remaining 2: 60 to 69 patterns remaining 1: Pattern With less than 60 remaining

(Development speed evaluation)
In the spray development at the time of the evaluation of the adhesiveness, the time during which a pattern can be formed without any development residue was defined as the development dissolution time, and the evaluation was performed according to the following 5 grades. Below 2 is a level that is difficult to use.
5: Development dissolution time is less than 40 s 4: Development dissolution time is 40 s or more and less than 50 s 3: Development dissolution time is 50 s or more and less than 60 s 2: Development dissolution time is 60 s or more and less than 70 s 1: Development dissolution time is 70 s or more. Or, if the pattern does not peel and remain for less than 70 s

(Pattern shape evaluation)
The cross section of the pattern of the 100 μm photomask portion of the filter segment formed by the above method was observed and evaluated using an electron microscope. The cross section of the pattern has a good forward taper. The evaluation ranks are as follows.
5: Forward tapered shape with a gentle cross section 3: Forward tapered shape with a cross section 1: Reverse tapered shape with a cross section

Claims (5)

A colorant, a dispersant, a photopolymerizable compound, a photopolymerization initiator, a photosensitive coloring composition containing a solvent,
An ethylenic dispersant containing an aromatic carboxyl group-containing resin (A) and an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of a trivalent or higher polyvalent mercaptan compound (s1) A photosensitive coloring composition containing a basic resin (B) which is a polymer obtained by polymerizing an unsaturated monomer (b). The photosensitive coloring composition according to claim 1, wherein the trivalent or higher polyvalent mercaptan compound (s1) is a thiocarboxylic acid derivative. The tertiary amino group in the ethylenically unsaturated monomer (b1) having a tertiary amino group is a group selected from the group consisting of a group represented by the following general formula (1) and a dialkylamino group. Or the photosensitive coloring composition according to 2.
General formula (1)
[In the general formula (1),
R ²⁰¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical group or OR ²⁰³ ,
R ²⁰³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group,
R ²⁰² each independently represents an alkyl group having 1 to 8 carbon atoms,
* Represents a bond. ] The photosensitive coloring composition according to any one of claims 1 to 3, wherein the coloring agent is a halogenated phthalocyanine pigment. A color filter comprising a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 4 on a substrate.