JP2018091886A - Photosensitive coloring composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring composition which not only is excellent in low viscosity, storage stability, brightness and contrast but also achieves excellent adhesion, developability, pattern linearity and pattern shape, and to provide a color filter formed using the same.SOLUTION: A photosensitive coloring composition contains a coloring agent, a dispersion agent, a photopolymerizable compound, a photopolymerization initiator, and a solvent, where the dispersion agent contains an aromatic carboxyl group-containing resin (A) and a basic resin (B) obtained by polymerization of an ethylenically unsaturated monomer (b) containing an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of a tri- or higher polyvalent mercaptan compound (s1).SELECTED DRAWING: None

Description

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

  In a photosensitive composition for a color filter, a dispersant is generally used in order to keep a colorant in a well-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 type structure or a comb type 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 the production. In the case of a comb shape, a portion that becomes 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 remaining There is a method (see Patent Documents 2 and 3) in which a secondary amine is a functional group that adsorbs to the pigment surface.

  Also proposed is a method of maintaining a good dispersion state of the pigment by using a dispersant having an acidic functional group and a basic resin that is not structure-controlled without using a structure-controlled dispersant. (See Patent Documents 4 to 6). However, although the basic resin described here has high refining ability and dispersion stability, it has high oil solubility, so the alkali developability (solubility in the developer) is very poor, resulting in poor alkali developability. Defects in the linearity and shape of the derived pattern pixels have also occurred, and there is a strong demand for improvements in these characteristics.

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

  This invention makes it a subject to achieve the following objectives. That is, the object of the present invention is not only low viscosity, storage stability, lightness and contrast, but also a photosensitive coloring composition having both excellent adhesion, developability, pattern linearity and pattern shape. And a color filter formed using the same.

  As a result of intensive studies to solve the above problems, the present inventors have used a branched basic resin synthesized in the presence of a specific compound as a photosensitive coloring composition for a color filter. The present inventors have found that a color filter excellent in dispersibility, stability, heat resistance, developability, and resolution can be produced, and have led to the present invention.

That is, the present invention is a photosensitive coloring composition comprising a colorant, a dispersant, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The dispersant contains an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of the aromatic carboxyl group-containing resin (A) and 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).

  Moreover, this invention relates to the said photosensitive coloring composition whose polyvalent mercaptan compound (s1) more than trivalence is a thiocarboxylic acid derivative.

  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. It is related with the said photosensitive coloring composition which is.

General formula (1)
[In 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 a 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, and * represents a bond. ]

  The present invention also relates to the photosensitive coloring composition, wherein the colorant is a halogenated phthalocyanine pigment.

  Furthermore, this invention relates to the color filter characterized by comprising the filter segment formed from the said photosensitive coloring composition on a base material.

  The photosensitive coloring composition of the present invention is a photosensitive coloring composition comprising a colorant, a dispersant, a photopolymerizable compound, a photopolymerization initiator, and a solvent, wherein the dispersant is an aromatic carboxyl. 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) ) Polymerized basic resin (B), not only has low viscosity, storage stability, brightness and contrast, but also achieves adhesion, developability, pattern linearity and pattern shape. It is characterized by doing.

  Hereinafter, the present invention will be described in detail. In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent. Further, “CI” mentioned in the present specification means a 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 the molecule. Particularly preferred is a (meth) acrylic dispersant. The weight average molecular weight of the resin is preferably 2000 to 35000, more preferably 4000 to 25000, still more preferably 6000 to 20000, and particularly preferably 7000 to 15000. The acid value of the resin is preferably 5 to 200. More preferably, it is 10-150, More preferably, it is 15-100, Most preferably, it is 20-80. Among these, 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 anhydride and / or aromatic tetracarboxylic dianhydride. The product is preferably a resin. The resin (a) can be produced by a known method such as WO2008 / 007776, but 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. More preferably. For example, a polymer having two hydroxyl groups at one end as a preferred example 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. Can be obtained. The hydroxyl group of the polymer having a hydroxyl group reacts with an acid anhydride group of an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring opens, This produces 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 aromatic tetracarboxylic dianhydride. Preferably, the resin is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of the product. 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 group can be used. A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product with an acid anhydride and / or an acid anhydride group of an aromatic tetracarboxylic dianhydride is preferable.

≪Compound with 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, Examples include 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

≪Aromatic tricarboxylic dianhydride≫
The aromatic tricarboxylic dianhydride in the present invention may have any structure as long as it has one carboxylic 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, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenylsulfo Tricarboxylic anhydride and the like.

≪Aromatic tetracarboxylic dianhydride≫
The aromatic tetracarboxylic dianhydride in the present invention may have any structure as long as it has two carboxylic 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 to 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 which 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 General Formula (4) and 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 General Formula (7) and General Formula (8), * 4 represents a bond with T1 on the U1 side, * 5 represents a bond with A3 or T1 on the A3 side in the repeating unit, * 6 represents a bond to A1, * 7 represents a bond to 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 General Formula (11) and General Formula (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 1-20. ]

  The weight average molecular weight of the vinyl polymer portion P of the resin represented by the general formula (2) is preferably 100 to 30000 in order to achieve both the viscosity stability and chemical resistance of the dispersion, and more preferably the weight average molecular weight. 200-10000.

  The weight average molecular weight of the resin represented by the general formula (2) is preferably 1000 to 50000 in order to achieve both the viscosity stability and chemical resistance of the dispersion, and more preferably the weight average molecular weight is 200 to 30000.

  When the resin represented by the general formula (2) is used as a pigment composition for a color filter, as a colorant adsorbing group and a carboxyl group that functions as an alkali-soluble group during 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 obtained mainly by two reactions of an ethylenically unsaturated double bond polymerization reaction and a chain transfer reaction, and is represented by a general formula (structure). Since it is impossible or not practical, it is 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. What is 3-10 is preferable. The number of thiol groups in one molecule may differ, for example, between a low molecular compound and a high molecular compound, but is usually 3 to 10, preferably 3 to 6, and more preferably 3 to 4. It can be determined appropriately within a range. Two or more polyvalent mercaptan compounds (s1) may be used in combination.

   Further, the trivalent or higher polyvalent mercaptan compound (s1) contains primary, secondary and tertiary thiols, but preferably contains primary thiols from the viewpoint of improving adhesive strength. The molecular weight of the trivalent or higher polyvalent mercaptan compound (s1) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 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, and more preferably 300 or more.

  Examples of the polyvalent mercaptan compound (s1) include an aliphatic polythiol that may contain a heteroatom and an aromatic polythiol that may contain a heteroatom. From the viewpoint of improving the adhesive force, an aliphatic polythiol that may contain a hetero atom is preferable. Here, the “aliphatic polythiol optionally containing a heteroatom” means an aliphatic compound having a heteroatom having two or more thiol groups in one molecule. The “aromatic polythiol optionally containing a heteroatom” refers to an aromatic compound which may contain a heteroatom having two or more thiol groups in one molecule. The heteroatoms are preferably at least one selected from oxygen, nitrogen, sulfur, phosphorus, halogen and silicon, and more preferably from oxygen, nitrogen, sulfur, phosphorus and halogen, from the viewpoint of improving adhesive strength. It is at least one selected, and particularly preferably at least one selected from oxygen, nitrogen and sulfur.

<< Aliphatic polythiols optionally containing heteroatoms >>
Examples of the aliphatic polythiol that may contain a heteroatom include polythiols in which a portion other than a thiol group is an aliphatic hydrocarbon such as alkanedithiol having 2 to 20 carbon atoms, and halogens of halohydrin adducts of alcohols. Polythiol formed by substituting atoms with thiol groups, polythiol composed of hydrogen sulfide reaction products of polyepoxide compounds, thioglycolic acid obtained by esterification of polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule with thioglycolic acid An esterified product, a mercapto fatty acid esterified product obtained by esterification of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule and a mercapto fatty acid, a thiol isocyanurate compound obtained by reacting an isocyanurate compound and a thiol, a polysulfide group Contains thio Le, silicones modified with thiol groups, modified silsesquioxane and the like with a thiol group.

  Examples of the polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule include 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 a heteroatom, the polythiol other than the thiol group is an aliphatic hydrocarbon, and the halogen atom of the halohydrin adduct of alcohol is a thiol group from the viewpoint of improving adhesive strength Preferred are polythiols substituted with hydrogen sulfide, polythiols consisting of hydrogen sulfide reaction products of polyepoxide compounds, thioglycolic acid esterified products, mercapto fatty acid esterified products, and thiol isocyanurate compounds, and more preferred are mercapto fatty acid esterified products and thiol isocyanurate compounds. Mercapto fatty acid esterified products are particularly preferred. From the same viewpoint, a thiol containing no polysulfide group or siloxane bond is also preferred.

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

(Mercapto fatty acid esterified product)
As the mercapto fatty acid ester product, a β-mercapto fatty acid ester product having a primary thiol group is preferable from the viewpoint of improving adhesive strength, and a β-mercaptopropionic acid of a polyhydric alcohol having 2 to 6 hydroxyl groups in the molecule. An esterified product is more preferable. In addition, the mercapto fatty acid esterified product having a primary thiol group preferably has 4 to 6 thiol groups in one molecule from the viewpoint of improving adhesive strength, and is preferably 4 or 5. Preferably, it is four.

  The β-mercaptopropionate esterified product 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.

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

<Polythiol where the portion other than the thiol group is an aliphatic hydrocarbon>
Examples of the polythiol in which the portion other than the thiol group is an aliphatic hydrocarbon include alkanedithiol having 2 to 20 carbon atoms. Examples of the alkanedithiol having 2 to 20 carbon atoms include 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- And cyclohexanedithiol.

[Ethylenically unsaturated monomer (b)]
The basic resin (B) of the present invention contains an ethylenically unsaturated monomer (b1) having a tertiary amino group and, if necessary, another ethylenically unsaturated monomer (b2). It can be obtained by polymerizing the saturated monomer (b).
<< Ethylenically unsaturated monomer (b1) having tertiary amino group >>
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 selected from the group consisting of a group represented by the following general formula (11), a dimethylamino group and a diethylamino group, and 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).
Formula (11)

[In 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 a 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, 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 include a methyl group, an ethyl group, and 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. 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, 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 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 include a methyl group, an ethyl group, and 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. A C1-C3 alkyl group is preferable.

Specific examples of the ethylenically unsaturated monomer (b1) in which the tertiary amino group is represented by the general formula (11) include compounds represented by the following general formulas (a-1) to (a-11). I can list them. R ²⁰⁴ in the general formulas (a-1) to (a-11) represents a hydrogen atom or a methyl group.

  Among these, 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 colorant 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 coloring composition for a color filter of the present invention, for example, an azo pigment, an azo metal complex pigment, a phthalocyanine pigment, an azomethine pigment, a quinacridone pigment, an isoindolinone pigment, Isoindoline pigments, quinophthalone pigments, perylene pigments, perinone pigments, dioxazine pigments, triarylmethane pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ansanthrone pigments, indance Examples include Ron pigments, flavanthrone pigments, pyranthrone pigments, squarylium pigments, and diketopyrrolopyrrole pigments.
The following are typical pigments and dyes that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include 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, 208,209,210,216,220,221,224,226,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Red dyes such as xanthene, azo, disazo, anthraquinone, and dipyrromethene can also be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

  Examples of yellow pigments that can be used in the present invention include 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 pigment described in Japanese Patent No. 4999326 Although it is mentioned, it is not particularly limited to these. Also, yellow dyes such as quinoline, azo, methine, coumarin, and isoindoline can be used.

  Examples of the green pigment that can be used in the present invention include C.I. I. Pigment Green 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, JP 2006-57635 A, International Publication No. 2015/118720. Examples include zinc phthalocyanine pigments described in pamphlet No. 4893859, and aluminum phthalocyanine pigments described in JP-A-2006-153481, etc., but are not particularly limited thereto. In addition, blue-green dyes such as triarylmethane, phthalocyanine, and squarylium can be used.

  Examples of blue pigments that can be used in the present invention include 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 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not 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, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned, but not limited thereto.

  The coloring composition for a color filter of the present invention includes metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, and 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 colorant used in the coloring composition of the present invention, a halogenated phthalocyanine pigment is preferable from the viewpoint of excellent brightness and contrast of a green pixel. Examples of the halogenated phthalocyanine pigment include C.I. I. And CI Pigment Green 7, 36, 58, JP-A-2006-57635, JP-A-2006-153481. Among these, from the viewpoint of brightness, the central metal is preferably zinc or aluminum, and further, an aluminum halide phthalocyanine pigment represented by the following general formula (100) and C.I. I. One type selected from the group consisting of CI Pigment Green 58 is more preferable. The basic resin (B) having a specific structure, which will be described in detail later, effectively works to disperse the aluminum phthalocyanine pigment, and can maximize 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 halogen atoms 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 that may have a substituent, an aryl group that may have a substituent, an alkoxyl group that may have a substituent, or a substituent. The aryloxy group which may have a group is represented. R ¹⁰³ represents a hydrogen atom, an alkyl group that may have a substituent, a cycloalkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocycle that may have a substituent. Represents a cyclic group. R ¹⁰⁴ represents a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent. ]

Below, each substituent in General formula (100) is demonstrated.
Examples of the halogen include fluorine, bromine, chlorine, and iodine, and two or more kinds may be used in combination. Bromine and chlorine are preferred, and bromine (Br) is particularly preferred from the viewpoint of lightness.

Examples of the alkyl group in R ^{101 to} R ¹⁰⁴ include 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, and a stearyl group. , A linear or branched alkyl group such as 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 halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups such as methoxy group, aryl groups such as phenyl group and tolyl group, and nitro groups. Further, there may be a plurality of substituents. Accordingly, examples of the alkyl group having a substituent include, for example, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2-ethoxyethyl group, and 2-butoxy. Examples include an ethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like.

Examples of the aryl group in R ^{101 to} R ¹⁰⁴ include monocyclic aromatic hydrocarbon groups such as a phenyl group and a p-tolyl group, and condensed aromatic hydrocarbon groups such as a naphthyl group and an anthryl group. A hydrocarbon group is preferred. Moreover, a C6-C12 aryl group is preferable. Examples of the substituent of the aryl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryl group having a substituent, for example, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-dimethylaminophenyl group, Examples include 2-methyl-4-chlorophenyl group, 4-methoxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group and the like.

Examples of the alkoxyl group in R ¹⁰¹ and R ¹⁰² include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, neopentyloxy group, 2,3-dimethyl-3- Examples include linear or branched alkoxyl groups such as a pentyloxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, and 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 halogen atoms such as chlorine, fluorine and bromine, aryl groups such as alkoxyl groups, phenyl groups and tolyl groups, and nitro groups. 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 include ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group, benzyloxy group and the like.

Examples of the aryloxy group in R ¹⁰¹ and R ¹⁰² include an aryloxy group composed of a monocyclic aromatic hydrocarbon group such as a phenoxy group and a p-methylphenoxy group, and a condensed aromatic hydrocarbon such as a naphthaloxy group and an anthryloxy group. An aryloxy group comprising a group, and an aryloxy group comprising a monocyclic aromatic hydrocarbon group is preferred. Moreover, a C6-C12 aryloxy group is preferable. Examples of the substituent of the aryloxy group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, amino groups and nitro groups. Further, there may be a plurality of substituents. Therefore, as the aryloxy group having a substituent, for example, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, 2-methyl-4-chlorophenoxy group, etc. 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-butylcyclohexyl group, a bornyl group, an adamantyl group, and the like. A condensed aliphatic hydrocarbon group is mentioned. Moreover, a C5-C12 cycloalkyl group is preferable. Examples of the substituent of the cycloalkyl group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. 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 in R ¹⁰³ and R ¹⁰⁴ include aliphatic heterocyclic groups such as pyridyl group, pyrazyl group, piperidino group, pyranyl group, morpholino group, acridinyl group, and aromatic heterocyclic groups. Moreover, a C4-C12 heterocyclic group is preferable and a C5-C13 heterocyclic group is preferable. Examples of the substituent of the heterocyclic group having a substituent include halogen atoms such as chlorine, fluorine and bromine, alkyl groups, alkoxyl groups, hydroxyl groups, amino groups and nitro groups. 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, and an N-methylpyrrolyl group.

As 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 is an aryl group or substituent which may have a substituent. is preferably an aryloxy group which may have, both R ¹⁰¹ and R ¹⁰² is an aryl group or more preferably an aryloxy group, both R ¹⁰¹ and R ¹⁰² is a phenyl group or phenoxy group, More preferably it is. 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 number of halogen atoms 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 4-9. It is clear that when the halogen distribution width is 4 or more, the association between phthalocyanine molecules is remarkably suppressed, which greatly contributes to the increase in particle size due to the association between molecules, and further to the reduction in contrast. became. Here, the “halogen distribution width” is the distribution of the number of halogens substituted for the aluminum phthalocyanine pigment represented by the general formula (100). In the mass spectrum obtained by mass spectrometry, the halogen distribution width calculates the signal intensity (each peak value) of the molecular ion peak corresponding to each component, and the value (total peak value) obtained by integrating each peak value, The number of peaks having a ratio of each peak value to 1% or more with respect to the total peak value was counted as a halogen distribution width.

  In the present invention, the aluminum phthalocyanine pigment represented by the general formula (100) is [AlPc (Y)] Xn (2 ≦ n ≦ 16) (where Pc is a phthalocyanine ring, X is a halogen atom, and n is 2 to 2). In the case where the integers of 16 are respectively represented, as representative examples 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 limited to these. is not. Further, 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)). It is not limited to. Further, cyclized isomers of the exemplified compounds are also included as preferred examples of the present invention.

<Miniaturization of pigment>
When the colorant used for the color composition for color filter of the present invention is a pigment, it is preferably used after being made fine from the viewpoint of contrast. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult, and when the thickness is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

  The water-soluble organic solvent functions to wet 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 to be 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 milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the 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 pigment derivatives. Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP2003-167112, JP2004-091497, JP2004-307854, JP2007-156395, JP2008-094773, JP2008-094986 JP, 2009-095007, JP 2008-19591 JP, but it is not limited to be used those described in Japanese Patent No. 4585781 Patent Publication. The dye derivative may be added at the time of pigmentation such as a 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 is one that disperses, dyes, or penetrates a colorant, and includes a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

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

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

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 2,000 to 100,000, more preferably in the range of 3,000 to 20,000, in order to disperse the colorant preferably. The value of Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

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

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

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

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

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

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

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

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

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

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

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

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

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin. Examples of the thermosetting compound 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, phenolic compounds and / or resins, but the present invention is not limited thereto.

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

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, 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 monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill 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, Acetic acid Propyl, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that 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.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

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

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

  The blending 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. It is more preferable that

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

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

  The content of the photopolymerization initiator is preferably 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>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxy) Cicarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like. These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also 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 colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid 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. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 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 polyfunctional thiol content is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by weight, the sensitivity is too high and the resolution may be lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the colored composition from being oxidized and yellowing due to a thermal process during thermal curing 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 coating film transmittance 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. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , 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, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 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, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

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

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like 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 the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds 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- D Ru-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, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

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

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -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, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a kneader, a kneader, a coloring agent in a coloring agent carrier such as a dispersing agent, a binder resin, and / or a solvent, preferably together with a dispersing aid (a pigment derivative or a surfactant). It can be produced by finely dispersing 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 or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

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

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a dispersant, or a surfactant can be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition formed by dispersing the colorant in the colorant carrier using the dispersion aid has brightness, contrast, and storage stability. Good. The pigment derivative and the dispersant are as described above.

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

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

<Removal of coarse particles>
The colored composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.
<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment. The color filter of the present invention is such that 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.

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

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

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

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

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

The color filter of the present invention is bonded to a counter substrate using a sealant, and after injecting liquid crystal from an injection port provided in a seal portion, the injection port is sealed, and a polarizing film or a retardation film is formed on the substrate as necessary. A color liquid crystal display device is manufactured by pasting to the outside. This color liquid crystal display device includes Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Convencend Bend (OCB). ) Etc., and can be used in a liquid crystal display mode in which colorization is performed.

  Further, the color filter of the present invention can be used for producing a color imaging device, an organic EL display device, electronic paper, etc. in addition to a color liquid crystal display device.

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

(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. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and “TSK-GEL SUPER HZM-N” is connected in series to both packing materials, and the oven temperature is 40 The measurement was performed at a flow rate of 0.35 ml / min using a THF solution as an eluent at ° C. The sample was dissolved in 1 wt% of the above eluent and 20 microliters was injected. All molecular weights are polystyrene equivalent values.

(Binder resin and acid value of dispersant (A) having aromatic carboxyl group)
The resin acid value is a value obtained by converting the measured acid value (mgKOH / g) into a solid content according to the potentiometric titration method of JIS K0070.

(Average molecular weight of basic resin (B))
The number average molecular weight (Mn) and 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 polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an N, N-dimethylformamide solution of 10 mM LiBr.

(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 accordance with the method of ASTM D 2074 into a solid content.

(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 spectrometry of the pigment powder, the halogen content is 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) Was 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 the total peak value was 1% or more.

  Subsequently, pigments, dye derivatives, binder resin solutions, dispersants having an aromatic carboxyl group (A), basic resins (B), coloring compositions for color filters, and photosensitive coloring compositions used in Examples and Comparative Examples. The manufacturing method of a thing is demonstrated.

<Method for producing pigment and dye derivative>
(Production of zinc halide phthalocyanine pigment (PG-1))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 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. The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. A zinc fluoride phthalocyanine pigment (PG-1) was obtained. The average primary particle size was 32.5 nm.

(Production of aluminum halide phthalocyanine pigment (PG-2))
In a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the following formula (200), 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. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., 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 stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment in which 8.0 average bromine atoms were 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 phthalocyanine ring, and 15.8 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. 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 (Parisol Yellow K0961HD manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 65 ° C. for 8 hours. The kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight to obtain quinophthalone. A pigment (PY-1) was obtained. The average primary particle size was 29.0 nm.

(Production of dye derivative (H-1))
According to the synthesis method of Japanese Patent Application Laid-Open No. 2004-067715, a pigment derivative (H-1) was obtained.
Dye derivative (H-1)

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. As a catalyst required for the reaction of 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 25.0 parts of dicyclopentanyl methacrylate, 16 parts of methyl methacrylate and the precursor at this stage from the dropping tube at temperature. A mixture of 1.0 part of nitrile was added dropwise over 2.5 hours to conduct a polymerization reaction. Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as a catalyst required for the reaction of the precursor at this stage. Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. The added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces 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))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 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 0.1 part of 2′-azobisisobutyronitrile and 102 parts of PGMAc were added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. Subsequently, 3.2 parts of pyromellitic 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 reacted at 120 ° C. for 7 hours. I let you. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was completed 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. It was confirmed that 95% had reacted by solid content measurement. 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 reaction was performed at 120 ° C. for 7 hours. I let you. The acid value was measured to confirm that 98% or more of the acid anhydride had been 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))
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser and stirrer, 80 parts of 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 7 parts of methyl methacrylate, 8 parts of 2-hydroxyethyl methacrylate, benzyl Add 5 parts of acrylate, trimethylolpropane tris (3-mercaptopropionate); TMMP 4.0 parts, 0.1 part of 2,2′-azobis (2,4-dimethylvaleronitrile), 104 parts of PGMAc, and add 90 parts. The reaction was carried out at ° C for 10 hours. It was confirmed that 95% had reacted by solid content measurement. Thus, a basic resin (B-1) having a solid content of 50%, an amine value per solid content of 185 mg KOH / g, and a weight average molecular weight (Mw) of 10,100 was obtained.

(Production Example of Basic Resin (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) was synthesized. A solution was obtained.

(Production example of basic resin (B-11) not using polyvalent mercaptan compound)
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 50 parts of methoxypropyl acetate and heated to 110 ° C. while purging 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) 4 parts were added and stirred until uniform, then dropped into the reaction vessel over 2 hours, and then the reaction was continued for 3 hours at the same temperature. In this way, a basic resin (B-11) having a solid content of 50%, an amine value per solid content of 270 mg KOH / 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) was synthesized. 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: dimethylaminopropylacrylamide MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate BzA: Benzyl methacrylate

<Method for producing colored composition for color filter>
(Production Example of Colored Composition (CP-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. 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 Colored Composition (CP-2 to 16))
A colored composition (CP-2 to 16) was obtained in the same manner as the colored composition (CP-1) except that the types of the colorant 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.

(Contrast evaluation)
The coloring composition (CP-1 to 16) was applied to a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm, using a spin coater, and the number of rotations was changed so that the film thickness was 1.5 μm. A three-level coated substrate was produced. As drying conditions, heat treatment was performed at 70 ° C./20 minutes after coating, and further at 230 ° C./30 minutes. Furthermore, the film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.), and the contrast at a film thickness of 1.5 μm was determined from the three points of data by the primary correlation method. The contrast was evaluated according to the following five levels.
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)
About the obtained coloring composition, the initial viscosity in 25 degreeC was measured using the E-type viscosity meter ("ELD type viscosity meter" by the Toki Sangyo company). Subsequently, after storing in a thermostat at 40 ° C. for 2 weeks and accelerating with time, the viscosity after aging is measured by the same method as the above viscosity measurement, and the rate of change in viscosity before and after storage at 40 ° C. for 2 weeks is calculated. The evaluation was made in three stages according to the following criteria.
5: Viscosity change rate is ± 5% or less 4: Viscosity change rate is in the range of + 5% to + 10%, or −5% to −10% 3: Viscosity change rate is + 10% to + 15%, or − When the range is 10% to -15% 2: When the viscosity change rate is + 15% to + 20%, or When the range is -15% to -20% 1: When the viscosity change rate 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)
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter and produced the coloring composition (CY-1).
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 Parts Propylene glycol monomethyl ether acetate: 70.0 parts

[Example 1]
(Production of photosensitive coloring composition (CR-1))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (CR-1).
Colored composition (CP-1): 20.0 parts Colored composition (CY-1): PY138 Colored composition: 18.5 parts Acrylic resin solution 1: 10.5 parts Photopolymerizable monomer (Toagosei Co., Ltd.) Manufactured by “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 Parts 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 composition (CR-2 to 16))
Except having changed the kind of coloring composition as having described in Table 3, it carried out similarly to the photosensitive coloring composition (CR-1), and obtained the photosensitive coloring composition (CR-2-16).

[Example 11]
(Production of photosensitive coloring composition (CR-11))
A mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1.0 μm filter to obtain a green photosensitive coloring composition (CR-11).
Colored composition (CP-11): 28.5 parts Colored composition (CY-1): PY138 Colored composition: 10.0 parts Acrylic resin solution 1: 10.5 parts Photopolymerizable monomer (Toagosei Co., Ltd.) Manufactured by “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 Parts 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) is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, and the solvent is heated by heating at 70 ° C. for 15 minutes in a clean oven. Removal was obtained. Subsequently, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed with an integrated light amount of 200 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Subsequently, after heating and cooling for 30 minutes at 230 ° C. in a clean oven, the brightness Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The green coated substrate was adjusted to chromaticity (x = 0.270, y = 0.580) with a C light source after heat treatment at 230 ° C. The alkali developer is composed of sodium carbonate 1.5% by weight, sodium hydrogen carbonate 0.5% by weight, an anionic surfactant ("Perrex NBL" manufactured by Kao Corporation) 8.0% by weight and water 90% by weight. Was used. The brightness was evaluated according to the following five levels.
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)
A substrate coated with a photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at a rotation speed of 2 μm after drying is dried at 70 ° C. for 20 minutes. Ultraviolet light of 150 mJ / cm 2 was irradiated using a super high pressure mercury lamp through a photomask having 100 openings of 10 μm × 10 μm. Subsequently, spray development was performed with an alkaline developer composed of a 0.2 wt% aqueous sodium carbonate solution to remove the unexposed portion, and then the substrate was washed with ion-exchanged water. At this time, the adhesion was evaluated based on how many 10 μm × 10 μm patterns remained. The developability evaluation was determined according to the following criteria.
5: More than 90 patterns remain 4: 80-89 patterns remain 3: 70-79 patterns remain 2: 60-69 patterns remain 1: Pattern Less than 60 remaining

(Development speed evaluation)
In the spray development at the time of the adhesion evaluation, the time required for pattern formation without developing residue was defined as the development dissolution time, and the evaluation was performed in the following five stages. 2 or less is a difficult level to use.
5: Development dissolution time is less than 40 s 4: Development dissolution time is from 40 s to less than 50 s 3: Development dissolution time is from 50 s to less than 60 s 2: Development dissolution time is from 60 s to less than 70 s 1: Development dissolution time is 70 s or more. Or, if the pattern does not peel off even after less than 70s

(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 evaluated by observation using an electron microscope. The pattern cross section has good forward taper. The rank of evaluation is as follows.
5: Forward tapered shape with gentle cross section 3: Forward tapered shape with cross section 1: Reverse tapered shape with cross section

Claims (5)

A photosensitive coloring composition comprising a colorant, a dispersant, a photopolymerizable compound, a photopolymerization initiator, and a solvent,
The dispersant contains an ethylenically unsaturated monomer (b1) having a tertiary amino group in the presence of the aromatic carboxyl group-containing resin (A) and a trivalent or higher polyvalent mercaptan compound (s1). The photosensitive coloring composition containing the basic resin (B) which is a polymer which polymerized the 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. 2. 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 of 2.
General formula (1)
[In 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,
Each of R ²⁰² independently represents an alkyl group having 1 to 8 carbon atoms;
* Represents a bond. ]   The photosensitive coloring composition according to claim 1, wherein the colorant 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.