TW202402820A - Colored resin composition, cured product, color filter, and image display device - Google Patents

Abstract

Provided is a colored resin composition having a high dissolution rate in a developer even when a pre-baking temperature is low. This colored resin composition contains (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, the colored resin composition being characterized in that the coloring agent (A) contains a yellow colorant and a phthalocyanine compound having a specific chemical structure, and the content ratio for the phthalocyanine compound in the (A) colorant is a specific ratio.

Description

Colored resin composition, hardened material, color filter and image display device

The present invention relates to a colored resin composition, a cured product, a color filter, and an image display device. This case claims priority based on Special Application No. 2022-040964 filed in Japan on March 16, 2022, and its contents are incorporated into this article.

Conventionally, as methods for manufacturing color filters used in liquid crystal display devices and the like, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods have been known. Among them, the pigment dispersion method, which has excellent properties on average, is most widely used from the viewpoints of spectral characteristics, durability, pattern shape, and accuracy.

In recent years, color filters have been required to have higher brightness, higher contrast, and higher color gamut. As a colorant that determines the color of a color filter, pigments are usually used in terms of heat resistance, light resistance, etc. However, pigments cannot meet market requirements, especially in terms of high brightness, so dyes are used instead of pigments. Research on color materials is in full swing. For example, the use of phthalocyanine-based dyes for green pixel applications is being studied (for example, see Patent Document 1). [Prior technical documents] [Patent documents]

[Patent Document 1] International Publication No. 2020/171060

[Problem to be solved by the invention]

The inventors of the present invention conducted research and found that the solubility of the colored resin composition described in Patent Document 1 in the developer greatly changes depending on the content ratio of the phthalocyanine dye in the colorant. When the content ratio of the above-mentioned phthalocyanine dye is low, the dissolution speed in the developer becomes slow. It was also found that this tendency is significant especially when the prebaking temperature is low. Furthermore, it was also found that in the colored resin composition described in Patent Document 1, depending on the content ratio of the phthalocyanine-based dye in the colorant, there is a risk of residue after development or a change in the contrast of the green pixels obtained. Worry.

Therefore, the object of the present invention is to provide a colored resin composition that has a faster dissolving speed in the developer and a higher production efficiency even when the prebaking temperature is low. Furthermore, an object of the present invention is to provide a colored resin composition that suppresses the generation of residues and obtains green pixels with excellent contrast. [Technical means to solve problems]

The present inventors conducted intensive research and found that the above-mentioned problems can be solved by setting the content ratio of a specific phthalocyanine compound in the colorant to a specific ratio or more, and thus completed the present invention. That is, the present invention has the following constitution.

[1] A colored resin composition characterized by containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) photopolymerizability A monomer, and the above-mentioned (A) colorant contains a phthalocyanine compound and a yellow colorant having a chemical structure represented by the following general formula (1), and the content ratio of the above-mentioned phthalocyanine compound in the above-mentioned (A) colorant is: 65 mass% or more and 90 mass% or less.

[Chemical 1]

(In formula (1), A ¹ to A ¹⁶ each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2); wherein, at least one of A ¹ to A ¹⁶ represents a fluorine atom, and One or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2))

[Chemicalization 2]

(In formula (2), The content ratio of the phthalocyanine compound in the colorant (A) is 70% by mass or more and 90% by mass or less. [3] The colored resin composition according to [1] or [2], wherein the halogen atoms of A ¹ to A ¹⁶ in the above formula (1) are fluorine atoms. [4] The colored resin composition according to any one of [1] to [3], wherein in the above formula (1), at least one of A ¹ to A ⁴ is a fluorine atom, and one of A ⁵ to A ⁸ The above are fluorine atoms, at least one of A ⁹ to A ¹² is a fluorine atom, and at least one of A ¹³ to A ¹⁶ is a fluorine atom. [5] The colored resin composition according to any one of [1] to [4], wherein the benzene ring in the above formula (2) has an alkoxycarbonyl group. [6] The colored resin composition according to any one of [1] to [5], wherein X in the above formula (2) is an oxygen atom. [7] The colored resin composition according to any one of [1] to [6], wherein in the above formula (1), at least one of A ¹ to A ⁴ is a group represented by the above formula (2), A One or more of ⁵ to A ⁸ is a group represented by the above formula (2), one or more of A ⁹ to A ¹² is a group represented by the above formula (2), and one or more of A ¹³ to A ¹⁶ is The base represented by the above formula (2). [8] The colored resin composition according to any one of [1] to [7], wherein the above-mentioned yellow colorant is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 185, and a nickel couple represented by the following formula (i) At least one of the group consisting of nitrogen complexes.

[Chemical 3]

[9] The colored resin composition according to [1], wherein the content ratio of the yellow colorant in the colorant (A) is 10% by mass or more and 35% by mass or less. [10] The colored resin composition according to any one of [1] to [9], wherein the content ratio of the colorant (A) in the total solid content of the colored resin composition is 10 mass % or more and 80 mass % the following. [11] A hardened product obtained by hardening the colored resin composition according to any one of [1] to [10]. [12] A color filter having pixels produced using the colored resin composition according to any one of [1] to [10]. [13] An image display device having a color filter as in [12]. [Effects of the invention]

According to the present invention, even when the prebaking temperature is low, a colored resin composition can be provided that has a fast dissolving speed in the developer and has high production efficiency. Furthermore, according to the present invention, it is possible to provide a colored resin composition that suppresses the generation of residues and obtains green pixels with excellent contrast.

In the present invention, the "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography). In the present invention, the term "total solid content" refers to all components other than the solvent in the colored resin composition. Even if components other than the solvent are liquid at normal temperature, these components are not included in the solvent but are included in all solid components. In the present invention, the so-called "amine value", unless otherwise specified, means the amine value in terms of effective solid content, which is expressed by the mass of KOH equivalent to the amount of alkali in the solid content of the dispersant per 1 g. value. In the present invention, "C.I." refers to color index.

[1] Colored resin composition The colored resin composition of the present invention contains (A) colorant, (B) solvent, (C) alkali-soluble resin, (D) photopolymerization initiator, and (E) photopolymerizable monomer body. Furthermore, if necessary, other additives other than the above-mentioned components may be blended.

[1-1] (A) Coloring agent The (A) coloring agent contained in the colored resin composition of the present invention contains a phthalocyanine compound (hereinafter, sometimes referred to as It is "Phthalocyanine compound (1)") and yellow colorant. (A) The content ratio of the phthalocyanine compound (1) in the colorant is 65 mass% or more and 90 mass% or less.

[Chemical 4]

In formula (1), A ¹ to A ¹⁶ each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2); wherein, at least one of A ¹ to A ¹⁶ represents a fluorine atom, and A One or more of ¹ to A ¹⁶ represents a group represented by the following general formula (2).

[Chemistry 5]

In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. *Indicates bonding key.

The (A) coloring agent contained in the colored resin composition of the present invention contains the phthalocyanine compound (1), and the content ratio of the phthalocyanine compound (1) in the (A) coloring agent is 65 mass % or more and 90 mass % or less. In the phthalocyanine compound (1), at least one of the hydrogen atoms constituting the phthalocyanine skeleton is replaced by a fluorine atom with a smaller atomic radius, forming a structure that is less likely to hinder the aggregation of the phthalocyanine compounds (1). Therefore, by prebaking Aggregation is formed when the distance between molecules is shortened by heating during baking, thereby forming a complex in such a manner that the (C) alkali-soluble resin contained in the colored resin composition of the present invention is wound around it. It is considered that it is similar to phthalein. The dissolution rate of the cyanine compound (1) becomes faster than when it is alone. At this time, if the prebaking temperature is low, it is difficult for the phthalocyanine compounds (1) to aggregate with each other. On the other hand, by setting the content ratio of the phthalocyanine compound (1) to 65% by mass or more, the aggregation of the phthalocyanine compounds (1) is less likely to be hindered by other colorants, even when the prebaking temperature is low. The phthalocyanine compound (1) also forms regular aggregates, which makes local aggregation less likely to occur. Therefore, the transmittance increases, the contrast becomes higher, and the molecular weight of the aggregate becomes larger, making it easier to wind the alkali-soluble resin. around it, it is believed that the dissolution speed becomes faster and the generation of residue during development is also suppressed.

(A ¹ to A ¹⁶ ) In the above formula (1), A ¹ to A ¹⁶ each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2). Among them, one or more of A ¹ to A ¹⁶ represents a fluorine atom, and one or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

[Chemical 6]

In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. *Indicates bonding key.

Examples of the halogen atom of A ¹ to A ¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of high brightness, a fluorine atom is preferred. Moreover, among A ¹ to A ¹⁶ , it is preferable that at least 1 fluorine atom is present, more preferably 6 or more fluorine atoms are used, still more preferably 7 or more fluorine atoms are used, particularly 8 or more fluorine atoms are used, and the number of fluorine atoms is 15 or less. , preferably 12 or less, more preferably 10 or less. By setting the value above the lower limit, the stability of the phthalocyanine compound (1) tends to be improved, and by setting it below the above upper limit, affinity with the dispersant or solvent in the colored resin composition exists. Sexual enhancement tendency. The above upper and lower limits can be combined arbitrarily. For example, the number of substituents representing fluorine atoms in A ¹ to A ¹⁶ is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and still more preferably 8 to 10.

(X) X in formula (2) represents a divalent linking group. The divalent connecting group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, and a -N(R ^a1 )- group (R ^a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). From the viewpoint of stability during baking, an oxygen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

(Substituents that the benzene ring may have) The benzene ring in formula (2) may have any substituents. The substituent is not particularly limited, and examples thereof include: a halogen atom, an alkyl group ( ^-RA group), an alkoxy group (-OR ^A group (where ^RA represents an alkyl group)), an alkoxycarbonyl group ( -COOR ^A group (where R ^A represents an alkyl group)), aryl group ( ^-RB group), aryloxy group (-OR ^B group (where R ^B represents an aryl group)), aryloxycarbonyl group (-COOR ^B group (where R ^B represents an aryl group)). From the viewpoint of development solubility or brightness, an alkoxycarbonyl group is preferred.

The alkyl group ( ^RA ) contained in these groups may be straight chain, branched, or cyclic. From the viewpoint of affinity with organic solvents, straight chain is preferred. The alkyl group. The number of carbon atoms in the alkyl group ( ^RA ) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less. By setting the value above the above lower limit, aggregation tends to be suppressed and foreign matter is suppressed, and by setting the value below the above upper limit, solvent affinity tends to be improved and stability over time tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 5, and still more preferably 2 to 4. Examples of the alkyl group ( ^RA ) include methyl, ethyl, propyl, butyl, pentyl, and hexyl. From the viewpoint of inhibiting aggregation, methyl or ethyl is preferred, and more preferred is Ethyl.

The aryl group ( ^RB ) contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The number of carbon atoms in the aryl group ( ^RB ) is not particularly limited, but is preferably 4 or more, more preferably 6 or more, and is preferably 12 or less, more preferably 10 or less, and still more preferably 8 or less. By setting the value above the lower limit, aggregation due to steric repulsion tends to be suppressed, and by setting the value below the upper limit, solvent affinity tends to be improved and stability over time tends to be improved. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, the carbon number of the aryl group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include benzene ring, naphthalene ring, pentacyclopentadiene ring, indene ring, azulene ring and  ring having one free atom valence. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, and a 1,3-ethazole ring having one free atom valence. , Isothiazole ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furoxin ring, pyridine ring, pyrimidine ring, pyrimidine ring, 1,3,5-tristriazole ring, benzene Furan ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indole ring, 2H-1-benzopiper Phenyl ring, 1H-2-benzopiran ring, quinoline ring, isoquinoline ring, 4H-quinoline Ring, benzimidazole ring, 1H-indazole ring, quinoline ring, quinazoline ring, 㖕line ring, pyridine ring, 1,8-㖠dine ring, purine ring, pteridine ring.

When the benzene ring in the formula (2) has any substituent, the number of substitutions is not particularly limited, and the dye molecules generate π-π stacking with each other to improve heat resistance and suppress the decrease in brightness caused by the decomposition of the dye. From this point of view, it is preferable that the number of substitutions per benzene ring is 1. When the benzene ring in formula (2) has any substituent, the substitution position may be ortho, meta, or para, from the viewpoint of stacking into the densest structure. , preferably counterpoint.

At least one of A ¹ to A ¹⁶ represents a fluorine atom. From the viewpoint of improving brightness by forming an aggregate between two molecules of the phthalocyanine compound (1), it is preferred that at least one of A ¹ to A ⁴ be a fluorine atom, and one of A ⁵ to A ⁸ The above are fluorine atoms, and at least one of A ⁹ to A ¹² is a fluorine atom, and at least one of A ¹³ to A ¹⁶ is a fluorine atom; more preferably, at least two of A ¹ to A ⁴ are fluorine atoms, and A Two or more of ⁵ to A ⁸ are fluorine atoms, two or more of A ⁹ to A ¹² are fluorine atoms, and two or more of A ¹³ to A ¹⁶ are fluorine atoms.

In formula (1), at least one of A ¹ to A ¹⁶ represents a group represented by formula (2). From the viewpoint of solubility in organic solvents or brightness, it is preferred that at least one of A ¹ to A ⁴ be a group represented by formula (2), and that at least one of A ⁵ to A ⁸ be a group represented by formula (2). As for the represented groups, at least one of A ⁹ to A ¹² is a group represented by formula (2), and at least one of A ¹³ to A ¹⁶ is a group represented by formula (2); more preferably, A ¹ to Two or more of A ⁴ are groups represented by formula (2), two or more of A ⁵ to A ⁸ are groups represented by formula (2), and two or more of A ⁹ to A ¹² are represented by formula (2). represents a group, and more than two of A ¹³ to A ¹⁶ are groups represented by formula (2). From the viewpoint of suppressing a decrease in brightness through efficient stacking, it is preferable that A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ and A ¹⁵ be represented by the formula (2) group, and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ and A ¹⁶ are halogen atoms; particularly preferred are A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ and A ¹¹ , A ¹⁴ , and A ¹⁵ are groups represented by formula (2), and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ , and A ¹⁶ are fluorine atoms.

Examples of the phthalocyanine compound (1) include the following compounds.

[Chemical 7]

In addition, in the above formula, Et represents an ethyl group.

[Chemical 8]

[Chemical 9]

[Chemical 10]

As a method for producing the phthalocyanine-based dye (1), a known method can be used. For example, the method described in Japanese Patent Application Laid-Open No. 05-345861 can be used.

The content ratio of the phthalocyanine compound (1) in the coloring agent (A) in the colored resin composition of the present invention is 65% by mass or more, preferably 70% by mass or more, based on the total solid content of the coloring agent (A). , and, it is 90 mass% or less, preferably 85 mass% or less, more preferably 80 mass% or less. By setting it to the above lower limit value or more, even when the prebaking temperature is low, the dissolution rate tends to become faster, and the adhesion with the substrate tends to become better. Furthermore, the contrast tends to become higher, and residues tend to be suppressed. Furthermore, by setting it below the above-mentioned upper limit, the chromaticity required for the color filter tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the phthalocyanine compound (1) in the coloring agent (A) in the colored resin composition is 65 to 90 mass %, preferably 70 to 90 mass %, based on the total solid content of the coloring agent (A). %, more preferably 70 to 85 mass %, still more preferably 70 to 80 mass %.

(A) The coloring agent contains a yellow coloring material in addition to the phthalocyanine compound (1). By making the coloring agent (A) contain a yellow colorant in addition to the phthalocyanine compound (1), the reproducibility of the color required for the green pixel tends to be achieved. Examples of yellow colorants include yellow pigments and yellow dyes.

Examples of yellow pigments include: C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 and the 1:1 ratio of azobarbituric acid and nickel represented by the following formula (i) A compound in which another compound is inserted into the complex or its tautomer (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

[Chemical 11]

Examples of other compounds to be inserted into the nickel azo complex represented by formula (i) include compounds represented by the following formula (ii).

[Chemical 12]

From the viewpoint of high brightness and high color gamut, the nickel azo complex represented by C.I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185 and formula (i) is preferred. More preferably, it is a nickel azo complex represented by C.I. Pigment Yellow 83, 138, 139, 180, 185 and formula (i).

Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazole carbazo dyes, quinphthalone dyes, and cyanine dyes. Specific examples thereof include specific compounds described in Japanese Patent Application Laid-Open No. 2010-168531. As yellow dyes, those classified as dyes by the dye index, examples of C.I. solvent dyes include: C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94 ,98,99,162,163. Examples of C.I. acid dyes include: C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 or derivatives thereof. Examples of C.I. direct dyes include: C.I. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95 , 98, 102, 108, 109, 129, 136, 138, 141 dyes. Examples of C.I. mordant dyes include C.I. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, and 65 dyes. Preferred are C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23 ,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112,113,114,116,119,123,128,134,135 ,138,139,140,144,150,155,157,160,161,163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204 ,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251,23,25,29,34,40,42,72,76,99,111 , 112, 114, 116, 163, 243 or their derivatives. From the viewpoint of suppressing dye decomposition during baking, C.I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 is preferred.

As the yellow colorant contained in the colorant (A), from the viewpoint of the reproducibility of the color required for green pixels, C.I. Pigment Yellow 138, 185, and nickel azozine represented by the formula (i) are preferred. compound, more preferably C.I. Pigment Yellow 138.

(A) Colorant In addition to the phthalocyanine compound (1) and the yellow colorant, other colorants may be included. Examples of other colorants include pigments and dyes. When the colored resin composition of the present invention is used for green pixels, for example, a green colorant using a green pigment or a green dye is preferred. Examples of green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, and 63. From the viewpoint of brightness, C.I. Pigment Green 58 is preferred. As a green dye, among those classified by the dye index, C.I. solvent dyes include, for example, C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. Examples of C.I. acid dyes include: C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. mordant green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53. From the viewpoint of suppressing dye decomposition during thermal baking, C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred.

The average primary particle diameter of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, particularly preferably 0.04 μm or less. When the pigment is micronized, for example, a solvent salt grinding method can be preferably used.

The content ratio of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but it is preferably 10 mass % or more, more preferably 15 mass % or more, based on the total solid content of the colored resin composition. It is preferably 20 mass% or more, more preferably 25 mass% or more, particularly preferably 30 mass% or more, and preferably 80 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% or less, preferably 40% by mass or less. By setting the value above the lower limit, a wider range of hues tends to be reproduced, and by setting the value below the upper limit, stability over time tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the colorant (A) in the colored resin composition is preferably 10 to 80 mass %, more preferably 15 to 80 mass %, and still more preferably 20 mass % in the total solid content of the colored resin composition. ~60 mass%, more preferably 25-50 mass%, particularly preferably 30-40 mass%.

The content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but it is preferably 1 mass % or more, more preferably 3 mass % or more, based on the total solid content of the colored resin composition. More preferably, it is 5 mass % or more, still more preferably 10 mass % or more, especially 15 mass % or more, and further preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass %. % or less, preferably 20 mass% or less. By setting the value above the lower limit, the brightness tends to be improved, and by setting the value below the upper limit, stability over time tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the phthalocyanine compound (1) in the colored resin composition is more preferably 3 to 50 mass %, more preferably 5 to 50 mass %, and still more preferably 3 to 50 mass % of the total solid content of the colored resin composition. It is 10-40 mass %, especially 15-30 mass %.

The yellow colorant in the total solid content of the colored resin composition of the present invention is preferably 2 mass% or more, more preferably 4 mass% or more, further preferably 6 mass% or more, and more preferably 25 mass% or less, more preferably 20 mass% or less, still more preferably 10 mass% or less. By setting the value above the lower limit, the color required for green pixels tends to be reproduced, and by setting the value below the upper limit, the dissolution rate tends to become faster, and the contrast tends to become higher. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a yellow colorant as another colorant, the content ratio of the yellow colorant in the total solid content of the colored resin composition is preferably 2 to 25% by mass, more preferably 4 to 25% by mass. 20% by mass, more preferably 6 to 10% by mass.

The content ratio of the yellow colorant in the colorant (A) is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and still more preferably 20% by mass. Quality% or more. Moreover, 35 mass % or less is preferable, and 30 mass % or less is more preferable. By setting the value above the lower limit, the color required for green pixels tends to be reproduced, and by setting the value below the upper limit, the dissolution rate tends to become faster, and the contrast tends to become higher. The above upper and lower limits can be combined arbitrarily. For example, when the colorant (A) contains a yellow colorant, the content ratio of the yellow colorant in the colorant (A) is preferably 5 to 35% by mass, and more preferably 10 to 35% by mass. 35% by mass, more preferably 15 to 30% by mass.

The mass-based content ratio of the phthalocyanine compound (1) to the yellow coloring material (phthalocyanine compound (1)/yellow coloring material) is preferably 1.8 or more, more preferably 2 or more, further preferably 2.3 or more, and more preferably Preferably it is 9 or less, more preferably 7 or less, still more preferably 6 or less. By setting the value above the lower limit, the dissolution rate tends to become faster, and by setting the value below the upper limit, the color required for the green pixels tends to be reproduced. The above upper and lower limits can be combined arbitrarily. For example, when the colorant (A) contains a yellow colorant, the mass-based content ratio of the phthalocyanine compound (1) to the yellow colorant (phthalocyanine compound (1)/yellow colorant) is preferably 1.8 to 9 , more preferably 1.8 to 7, still more preferably 1.8 to 6, still more preferably 2 to 6.

When the colored resin composition of the present invention contains other colorants, the content ratio is not particularly limited, but it is preferably 1 mass % or more, and more preferably 3 mass % or more in the total solid content of the colored resin composition. , more preferably 5 mass% or more, more preferably 7 mass% or more, especially 10 mass% or more, and preferably 30 mass% or less, more preferably 25 mass% or less, still more preferably 20 mass% mass% or less. By setting the value above the lower limit, a wider range of hues tends to be reproduced, and by setting the value below the upper limit, stability over time tends to be ensured. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains other colorants, the content ratio of the other colorants in the total solid content of the colored resin composition is preferably 1 to 30 mass %, more preferably 3 to 30 mass %. More preferably, it is 5-25 mass %, Still more preferably, it is 7-25 mass %, Even more preferably, it is 10-20 mass %.

[1-2] (B) Solvent (B) The solvent in the colored resin composition or pigment dispersion of the present invention has the following functions: (A) colorant, (C) alkali-soluble resin, (D) photopolymerization The starting agent, (E) photopolymerizable monomer, and other components are dissolved or dispersed to adjust the viscosity. (B) The solvent may be any solvent that can dissolve or disperse each component.

Examples of the solvent (B) include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monon-n. Butyl ether, propylene glycol tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, Glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

Of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diglyme glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether glycol dialkyl ethers; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Acid ester, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate Ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, acetic acid 3- Glycol alkyl ether acetates such as methyl-3-methoxybutyl ester;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, dipyl ether, ethyl isobutyl ether, and dihexyl ether; Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, and methoxymethyl pentanone; Ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Such monovalent or polyhydric alcohols; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and dicyclohexane;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene; Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyrate Ester, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3 -Chained or cyclic esters; Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; Halogenated hydrocarbons such as chlorobutane and chloropentane; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile.

Examples of commercially available solvents include: mineral sprit, Varsol#2, Apco#18 Solvent, Apco thinner, Socal Solvent No.1 and No.2, Solvesso#150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve, Ethyl Cellosolve Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, and diglyme (all are trade names). One type of these solvents may be used alone, or two or more types may be used in combination.

When pixels of a color filter are formed by photolithography, (B) the solvent is preferably a solvent with a boiling point of 100 to 200°C (under a pressure of 1013.25 [hPa]; all boiling points are the same below) . A solvent having a boiling point of 120 to 170°C is more preferred. Glycol alkyl ether acetates are preferred in terms of a good balance of coating properties, surface tension, etc. and high solubility of the constituent components in the composition.

Glycol alkyl ether acetates can be used alone or in combination with other solvents. As a solvent used together, glycol monoalkyl ethers are particularly preferred. From the viewpoint of the solubility of the constituent components in the composition, propylene glycol monomethyl ether is preferred. Glycol monoalkyl ethers have high polarity. If too much is added, the pigments tend to agglomerate and the viscosity of the colored resin composition obtained subsequently increases, and the storage stability tends to decrease. Therefore, glycol monoalkyl ethers are used in combination. In the case of ethers, the ratio of glycol monoalkyl ethers in (B) the solvent is preferably 5 to 30 mass %, more preferably 5 to 20 mass %.

As another aspect, a solvent having a boiling point of 150° C. or higher may be used together. The combined use of a solvent having a boiling point of 150° C. or higher makes it difficult for the colored resin composition to dry, but has the effect that the relationship between the constituent components in the pigment dispersion liquid is less likely to be damaged by rapid drying. When a solvent having a boiling point of 150° C. or higher is used in combination, the content ratio of the solvent having a boiling point of 150° C. or higher in the (B) solvent is preferably 3 to 50 mass %, more preferably 5 to 40 mass %, especially Preferably, it is 5 to 30% by mass. By setting the value above the lower limit, for example, there is a tendency to easily prevent the colorant component from precipitating and solidifying at the tip of the slit nozzle, thereby causing foreign matter defects, and by setting the value below the above upper limit, there is a tendency to easily avoid Avoid slowing down the drying speed of the composition, which may cause problems such as poor tact in the vacuum drying process or pore marks in pre-baking. The solvent with a boiling point of 150°C or above may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, there is no need to additionally contain a solvent with a boiling point of 150°C or above. Preferable examples of solvents having a boiling point of 150° C. or higher include: diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3- Butanediol diacetate, 1,6-hexanol diacetate, glycerol triacetate.

When forming pixels of a color filter by an inkjet method, a suitable solvent (B) is one whose boiling point is preferably from 130°C to 300°C, more preferably from 150°C to 280°C. By setting it as above the said lower limit value, the uniformity of the coating film obtained tends to become good, and by setting it as below the said upper limit value, there exists a tendency that the residual solvent at the time of baking can be easily reduced. The vapor pressure of the solvent is preferably 10 mmHg or less, more preferably 5 mmHg or less, and still more preferably 1 mmHg or less, from the viewpoint of the uniformity of the coating film obtained.

In the manufacturing of color filters by the inkjet method, the ink ejected from the nozzle is very fine, ranging from several picoliters (pL) to tens of picoliters. Therefore, solvent exists before it is sprayed around the nozzle or into the pixel array. Evaporation causes the ink to concentrate and dry out. In order to avoid this situation, it is preferable that the solvent (B) contains a solvent with a relatively high boiling point. Specifically, it is preferable that the solvent (B) contains a solvent with a boiling point of 180° C. or higher. More preferably, it contains a solvent with a boiling point of 200°C or higher, and even more preferably, it contains a solvent with a boiling point of 220°C or higher. When a solvent with a boiling point of 180°C or higher is contained, the content ratio of the solvent with a boiling point of 180°C or higher in the solvent (B) is preferably 50 mass% or more, more preferably 70 mass% or more, and most preferably 90 mass% or more. . By setting it to the above-mentioned lower limit value or more, there is a tendency that the effect of preventing evaporation of the solvent from the liquid droplets can be easily exerted.

Examples of solvents having a boiling point of 180°C or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3-butanediol. Diacetate, 1,6-hexanol diacetate, glycerol triacetate. In order to adjust the viscosity of the colored resin composition or adjust the solubility of the solid component, a solvent with a boiling point lower than 180°C may be included. As such a solvent, a solvent with low viscosity, high solubility, and low surface tension is preferred. For example, ethers, esters, and ketones are preferred. For example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferred.

If the solvent contains alcohol, the ejection stability in the inkjet method may be deteriorated. When alcohols are used together, the content ratio of alcohols in (B) the solvent is preferably 20 mass% or less, more preferably 10 mass% or less, and particularly preferably 5 mass% or less.

(B) The content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit is preferably 99 mass% or less, more preferably 90 mass% or less, and still more preferably 85 mass% or less. By setting it to below the above-mentioned upper limit, there is a tendency for the coating film to be easily formed. On the other hand, the lower limit of the solvent content ratio is preferably 70 mass% or more, more preferably 75 mass% or more, and still more preferably 80 mass% or more, taking into consideration the viscosity suitable for coating. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the solvent in the colored resin composition is preferably 70 to 99 mass%, more preferably 75 to 90 mass%, and still more preferably 80 to 85 mass%.

[1-3] (C) Alkali-soluble resin The colored resin composition of the present invention contains (C) alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility in a developer. As (C) the alkali-soluble resin, for example, Japanese Patent Application Laid-Open No. 1997-207211, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, and Japanese Patent Application Laid-Open No. 11-140144 Publications, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 2000-56118, and Japanese Patent Laid-Open No. 2003-233179 are known polymer compounds described. Preferable examples include the following resins (C-1) to (C-5). (C-1): For a copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers, an unsaturated monobasic acid is added to at least part of the epoxy groups of the copolymer. The resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction (hereinafter may be referred to as "resin (C-1)") (C-2): A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as "resin (C-2)") (C-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl moiety of the above-mentioned resin (C-2) (hereinafter sometimes referred to as "resin (C-3)") (C-4): (meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)") (C-5): Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)"). Particularly preferred examples include resin (C-1).

The resins (C-2) to (C-5) only need to be soluble in an alkaline developer and have a solubility sufficient to complete the target development process. Japanese Patent Application Laid-Open No. 2009-025813 can be preferably used. Resin described as the same item in the gazette.

(C-1): For a copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers, an unsaturated monobasic acid is added to at least part of the epoxy groups of the copolymer. A resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction. One of the preferred aspects of the resin (C-1) is: "5 to 90 mol% of epoxy group-containing (meth)acrylate and 10 to 95 mol% of other radically polymerizable monomers. % copolymer, a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol % of the epoxy groups of the copolymer, or 10 to 10 mol % of the hydroxyl groups generated by the addition reaction Alkali-soluble resin obtained by adding polybasic acid anhydride to 100 mol%.

Examples of the epoxy group-containing (meth)acrylate include: (glycidylmeth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (3,4-(meth)acrylate). Epoxycyclohexyl)methyl ester, (meth)acrylic acid 4-hydroxybutyl glycidyl ether. Among them, glycidyl (meth)acrylate is preferred. One type of these epoxy group-containing (meth)acrylates may be used alone, or two or more types may be used in combination.

As another radically polymerizable monomer copolymerized with the epoxy group-containing (meth)acrylate, a mono(meth)acrylate having a structure represented by the following general formula (V) is preferred.

[Chemical 13]

In formula (V), R ⁹¹ to R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Furthermore, R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ may be connected to each other to form a ring. In formula (V), the ring formed by connecting R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ is preferably an aliphatic ring, which may be saturated or unsaturated, and preferably has a carbon number of 5 to 6.

Among them, the structure represented by formula (V) is preferably a structure represented by the following general formula (Va), (Vb) or (Vc). By introducing these structures into an alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition is improved, and the use of the colored resin composition The tendency of the resulting pixels to increase in intensity.

One type of mono(meth)acrylate having a structure represented by formula (V) may be used alone, or two or more types may be used in combination.

[Chemical 14]

As the mono(meth)acrylate having a structure represented by formula (V), various known mono(meth)acrylates can be used as long as they have a structure represented by formula (V), and the following general mono(meth)acrylates are particularly preferred. Mono(meth)acrylate represented by formula (VI).

[Chemical 15]

In the formula (VI), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents the structure represented by the formula (V).

When the copolymer of an epoxy group-containing (meth)acrylate and other radically polymerizable monomers contains a repeating unit derived from a mono(meth)acrylate represented by formula (VI), the source The content ratio of the repeating units derived from the mono(meth)acrylate represented by the formula (VI) to the repeating units derived from other radically polymerizable monomers is preferably 5 to 90 mol %, and more preferably 10-70 mol%, preferably 15-50 mol%.

The radically polymerizable monomer other than the mono(meth)acrylate represented by the formula (VI) is not particularly limited, and examples thereof include: styrene, α-position, ortho-position, meta-position of styrene, Para-alkyl, nitro, cyano, amide, ester derivatives and other vinyl aromatics; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene and other diamines Alkenes; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, (meth) Second butyl acrylate, third butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ( 2-Methylcyclohexyl methacrylate, dicyclohexyl (meth)acrylate, isopropyl (meth)acrylate, adamantyl (meth)acrylate, propynyl (meth)acrylate, ( Phenyl methacrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, anthraquinone (meth)acrylate, sunflower ester (meth)acrylate, salyl (meth)acrylate, (meth)acrylate Furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, (meth)acrylate Toluyl acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoroethyl (meth)acrylate Fluoroisopropyl ester, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, (methyl) (Meth)acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl (meth)acrylate; (meth)acrylamide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-dimethylamide, Meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-diisopropylamide, (meth)acrylic acid Anthrylamide and other (meth)acrylamide; (meth)acrylamide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N- Vinyl compounds such as vinylpyrrolidone, vinylpyridine, vinyl acetate; diethyl methylmaleate, diethyl maleate, diethyl fumarate, Ikon Unsaturated dicarboxylic acid diesters such as diethyl acid; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide and other monomaleimines; N-(meth)acrylylphthalimide.

Among these other radically polymerizable monomers, from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition, styrene, benzyl (meth)acrylate, and monomaleic acid are preferred. amine. Containing any one derived from styrene, benzyl (meth)acrylate, or monomaleimide in the copolymer of epoxy group-containing (meth)acrylate and other radically polymerizable monomers In the case of repeating units, among the repeating units derived from other radically polymerizable monomers, repeating units derived from styrene, repeating units derived from benzyl (meth)acrylate, and monomaleyl The total content ratio of the repeating units of the imine is preferably 1 to 70 mol%, and more preferably 3 to 50 mol%.

The well-known solution polymerization method can be used in the copolymerization reaction of epoxy group-containing (meth)acrylate and other radically polymerizable monomers. The solvent used is not particularly limited as long as it is inert to radical polymerization, and commonly used organic solvents can be used. Examples of the solvent used in the solution polymerization method include: ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate; diethylene glycol monoalkyl ether acetate; Diethylene glycol monoalkyl ether acetates such as methyl ether acetate, carbitol acetate, butyl carbitol acetate; propylene glycol monoalkyl ether acetate; dipropylene glycol monoalkyl ether acetate Acetate esters such as esters; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol, etc.; triethylene glycol dialkyl ethers Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; 1,4-dioxane, tetrahydrofuran and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone ketones; hydrocarbons such as benzene, toluene, xylene, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; methyl lactate, ethyl lactate, lactic acid Lactic acid esters such as butyl ester; dimethylformamide, N-methylpyrrolidone. These solvents may be used alone, or two or more types may be used in combination.

The usage amount of the solvent used in the solution polymerization method is preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass relative to 100 parts by mass of the copolymer obtained. By setting the usage amount of the solvent within the above range, the molecular weight of the copolymer tends to be easily controlled. The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization. Commonly used organic peroxide catalysts or azo compound catalysts can be used. Examples of organic peroxide catalysts include: well-known classifications as ketone peroxide, peroxy ketal, hydrogen peroxide, diallyl peroxide, diyl peroxide, peroxy ester, peroxide Catalyst for dicarbonate.

Examples of the radical polymerization initiator used in the copolymerization reaction include: benzyl peroxide, dicumyl peroxide, diisopropyl peroxide, and di-tert-butyl peroxide. , tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tert-hexyl peroxy-2-ethylhexanoate, 1,1 -Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexyl-3 , 3-isopropyl hydroperoxide, tert-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, peroxydicarbonate bis (4-th Tributylcyclohexyl) ester, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, 1,1-bis(tertiary) Butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (third hexylperoxy) 3,3,5-trimethylcyclohexane.

Examples of the azo compound catalyst include azobisisobutyronitrile and azodimethamide. Among them, one or two or more radical polymerization initiators with appropriate half-lives are used depending on the polymerization temperature. The usage amount of the radical polymerization initiator is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass relative to 100 parts by mass of the total monomers used in the copolymerization reaction.

The copolymerization reaction can be carried out by dissolving the monomers and radical polymerization initiators used in the copolymerization reaction in a solvent and raising the temperature while stirring. Alternatively, the monomers added with the radical polymerization initiator can be added dropwise until the temperature rises. It can be carried out in a stirred solvent, or a radical polymerization initiator can be added to the solvent and the monomer can be added dropwise while the temperature is rising. Reaction conditions can be set according to the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth)acrylate and other radically polymerizable monomers preferably contains repeating units 5 derived from the epoxy group-containing (meth)acrylate. A copolymer of ~90 mol% and 10-95 mol% of repeating units derived from other radically polymerizable monomers; more preferably, it contains 20 repeating units derived from epoxy group-containing (meth)acrylate. A copolymer of ~80 mol% and 80-20 mol% of repeating units derived from other radically polymerizable monomers; particularly preferably a copolymer containing 30 ~ 30 mol% of repeating units derived from epoxy-containing (meth)acrylate. A copolymer of 70 mol % and 70 to 30 mol % of repeating units derived from other radically polymerizable monomers.

By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth)acrylate to not less than the above-mentioned lower limit, the addition amount of the following unsaturated monobasic acid or polybasic acid anhydride tends to become sufficient. By setting the content ratio of repeating units derived from other radically polymerizable monomers to the above lower limit value or more, heat resistance and strength tend to become sufficient. Then, the unsaturated monobasic acid (polymerizable component) and the polybasic acid anhydride (alkali-soluble component) are reacted with the epoxy group of the copolymer of the epoxy group-containing (meth)acrylate and other radically polymerizable monomers.

As the unsaturated monobasic acid added to the epoxy group, a known unsaturated monobasic acid can be used. For example, an unsaturated carboxylic acid having an ethylenically unsaturated double bond can be used. Examples of the unsaturated monobasic acid added to the epoxy group include: (meth)acrylic acid; crotonic acid; o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid; α-position Monocarboxylic acids such as (meth)acrylic acid substituted with a haloalkyl group, an alkoxy group, a halogen atom, a nitro group or a cyano group are preferably (meth)acrylic acid. One type of unsaturated monobasic acid may be used alone, or two or more types may be used in combination.

By adding an unsaturated monobasic acid to the epoxy group, polymerizability can be imparted to the resin (C-1). The unsaturated monobasic acid is added to the epoxy groups of the copolymer in an amount of, for example, 10 to 100 mol%, preferably 30 to 100 mol%, and more preferably 50 to 100 mol%. By making it the said lower limit value or more, the stability with time of a colored resin composition tends to become favorable. As a method of adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be used.

Furthermore, as the polybasic acid anhydride added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used. Examples of polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chloro-bridged anhydride and other binary anhydrides. Acid anhydrides; anhydrides of trivalent or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and biphenyl tetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. One type of these polybasic acid anhydrides may be used alone, or two or more types may be used in combination.

By adding a polybasic acid anhydride to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, alkali solubility can be imparted to the resin (C-1). The polybasic acid anhydride is added to the hydroxyl group generated by adding the unsaturated monobasic acid to the epoxy group of the copolymer, for example, 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30~80 mol%. By setting the value below the above upper limit, the residual film ratio during development tends to be good, and by setting it above the above lower limit, the solubility tends to become sufficient. As a method of adding a polybasic acid anhydride to the hydroxyl group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be used.

Furthermore, in order to improve the photosensitivity, after adding the polybasic acid anhydride, glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to part of the carboxyl group formed. In order to improve developability, a glycidyl ether compound that does not have a polymerizable unsaturated group may be added to a part of the generated carboxyl group.

Furthermore, both a glycidyl ether compound having a polymerizable unsaturated group and a glycidyl ether compound not having a polymerizable unsaturated group may be added. Examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group. Examples of commercially available glycidyl ether compounds that do not have a polymerizable unsaturated group include trade names "CENACOL EX-111", "CENACOL EX-121", and "CENACOL EX-141" manufactured by Nagase ChemteX Corporation. , "CENACOL EX-145", "CENACOL EX-146", "CENACOL EX-171", "CENACOL EX-192".

The structure of the resin (C-1) is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 or Japanese Patent Application Laid-Open No. 2001-89533. The weight average molecular weight in terms of polystyrene measured by GPC of the resin (C-1) is not particularly limited, but is preferably 3,000 to 100,000, particularly preferably 5,000 to 50,000. When the value is equal to or higher than the above-mentioned lower limit, the heat resistance or film strength tends to be improved, and when the value is equal to or below the above-mentioned upper limit, the solubility in the developer tends to be improved. As a standard for molecular weight distribution, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mw/Mn) of the resin (C-1) is preferably 2.0 to 5.0.

From the viewpoint of coating film curability upon ultraviolet exposure, among (C) alkali-soluble resins, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain is preferred. (c1) The partial structure including the side chain having an ethylenically unsaturated group of the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, as long as the coating film hardenability during ultraviolet exposure and alkali are taken into consideration From the viewpoint of alkali solubility during development, for example, it is preferable to have a partial structure represented by the following general formula (CI).

[Chemical 16]

In formula (CI), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. *Indicates bonding key.

Among the partial structures represented by the formula (CI), from the viewpoint of sensitivity or alkali developability, a partial structure represented by the following general formula (CI') is preferred.

[Chemical 17]

In formula (CI'), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue refers to a univalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid. , benzophenone tetracarboxylic acid, methyl hexahydrophthalic acid, endomethylene tetrahydrophthalic acid, chlorobridge acid, methyl tetrahydrophthalic acid, biphenyl tetracarboxylic acid. From the viewpoint of patterning properties, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and metacarboxylic acid. Trimellitic acid and biphenyltetracarboxylic acid, more preferably tetrahydrophthalic acid and biphenyltetracarboxylic acid. One type of these polybasic acids may be used alone, or two or more types may be used in combination.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CI), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by the formula (CI) is not particularly limited, but it is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 40 mol% or more, more preferably 50 mol% or more, most preferably 65 mol% or more, more preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less, most preferably 70 mol% or less. By setting the value above the lower limit, the curability of the coating film during ultraviolet exposure tends to be improved, and by setting the value below the upper limit, the alkali solubility during alkali development tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CI) in (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%. %, more preferably 30-85 mol%, still more preferably 40-80 mol%, even more preferably 50-75 mol%, most preferably 65-70 mol%.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CI'), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by the formula (CI') is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, and more preferably It is preferably 40 mol% or more, more preferably 50 mol% or more, most preferably 65 mol% or more, and more preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less, most preferably 70 mol% or less. By setting the value above the lower limit, the curability of the coating film during ultraviolet exposure tends to be improved, and by setting the value below the upper limit, the alkali solubility during alkali development tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by the formula (CI) in (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferably 10 to 95 mol%, more preferably 20 to 90 mol%. %, more preferably 30-85 mol%, still more preferably 40-80 mol%, even more preferably 50-75 mol%, most preferably 65-70 mol%.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CI), the other partial structures contained are not particularly limited, as long as the acrylic copolymer resin is dissolved in alkali during alkali development From the viewpoint of stability, for example, it is also preferable to have a partial structure represented by the following general formula (CII).

[Chemical 18]

In the formula (CII), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group.

(R ⁴ ) In formula (CII), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. Examples of the alkyl group of R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, especially 8 or more, and preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and further It is better to be below 14, and especially preferably below 12. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 3 to 16, still more preferably 5 to 14, and particularly preferably 8 to 12.

Examples of the alkyl group include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of developability, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, Carboxyl, acrylyl, methacrylyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

Examples of the aromatic ring group of R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, further preferably 20 or less, especially 18 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, further preferably 6 to 20, and particularly preferably 6 to 18. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, and pyrene ring. , benzopyrene ring, ring, three-fold benzene ring, acenaphthene ring, fluoranthene ring, and fluoranthene ring. The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, and pyrazole ring. , imidazole ring, dioxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furo Furan ring, thienofuran ring, benzisinozole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridine ring, pyrimidine ring, trisulfonate ring, quinoline ring, isoquinoline Phenoline ring, zeoline ring, quinoline ring, phenanthridine ring, phenidine ring, quinazoline ring, quinazolinone ring, azulene ring. From the viewpoint of developability, a phenyl ring group and a naphthyl ring group are preferred, and a phenyl ring group is more preferred. Examples of substituents that the aromatic ring group may have include: methyl, ethyl, propyl, methoxy, ethoxy, chlorine, bromo, fluoro, hydroxyl, amino, and epoxy groups. , oligoethylene glycol group, phenyl group, carboxyl group. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

Examples of the alkenyl group of R ⁴ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.

Examples of the alkenyl group include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 2-penten-1-yl. , 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl. From the viewpoint of developability, vinyl and allyl are preferred, and vinyl is more preferred.

Examples of substituents that the alkenyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferred, and more preferably Preferably it is an alkyl group.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CII), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by the formula (CII) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and particularly preferably 20 mol%. Mol% or more, and preferably 70 Mol% or less, more preferably 60 Mol% or less, further preferably 50 Mol% or less, particularly preferably 40 Mol% or less. By setting it as above the said lower limit value, alkali solubility tends to improve, and by setting it as below the said upper limit value, there exists a tendency for the storage stability of a colored resin composition to improve. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (CII) in (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferably 1 to 70 mol%, more preferably 5 to 60 mol%. %, more preferably 10-50 mol%, particularly preferably 20-40 mol%.

When the (c1) acrylic copolymer resin contains a partial structure represented by the formula (CI), as other contained partial structures, from the viewpoint of suppressing a decrease in brightness by improving heat resistance, it is preferable to contain the following: Describe the partial structure represented by general formula (CIII).

[Chemical 19]

In formula (CIII), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, or an optionally substituted alkyl group. An alkoxy group having a substituent, a thiol group, or a sulfide alkyl group which may have a substituent. t represents an integer from 0 to 5.

(R ⁶ ) In formula (CIII), R ⁶ represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, or an alkyl group which may have a substituent. Oxygen group, thiol group, or sulfide alkyl group which may have a substituent. Examples of the alkyl group for R ⁶ include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, still more preferably 14 or less, Especially preferably below 12. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 3 to 16, still more preferably 3 to 14, and particularly preferably 5 to 12.

Examples of the alkyl group include methyl, ethyl, cyclohexyl, dicyclopentyl, and dodecyl. From the viewpoint of heat resistance, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, Carboxyl, acrylyl, methacrylyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

Examples of the alkenyl group of R ⁶ include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.

Examples of the alkenyl group include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, and 2-penten-1-yl. , 3-penten-2-yl, hexenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl. From the viewpoint of exposure sensitivity during ultraviolet exposure, vinyl and allyl are preferred, and vinyl is more preferred.

Examples of substituents that the alkenyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

Examples of the alkynyl group of R ⁶ include linear, branched or cyclic alkynyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkynyl group is preferably 2 to 22, more preferably 2 to 20, still more preferably 2 to 18, still more preferably 2 to 16, and particularly preferably 2 to 14.

Examples of the alkynyl group include: 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4-pentadiyn-3-yl, 1,3-pentadiyn-5-yl, 1-hexyn-6-yl.

Examples of substituents that the alkynyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

Examples of the halogen atom of R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of storage stability of the acrylic copolymer resin, a fluorine atom is preferred.

Examples of the alkoxy group of R ⁶ include linear, branched or cyclic alkoxy groups. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, particularly preferably 12 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkoxy group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12.

Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group and isobutoxy group.

Examples of substituents that the alkoxy group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, and phenyl group. , carboxyl, acrylyl, methacrylyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

Examples of the sulfide alkyl group of R ⁶ include linear, branched or cyclic sulfide alkyl groups. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, particularly preferably 12 or less. When the value is equal to or higher than the above-mentioned lower limit, the lipophilicity tends to be improved and the solubility in the solvent is improved, and when the value is below the above-mentioned upper limit, the hydrophilicity is improved and the alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the sulfide alkyl group is preferably 1 to 20, more preferably 1 to 18, still more preferably 1 to 16, still more preferably 1 to 14, and particularly preferably 1 to 12.

Examples of the sulfide alkyl group include methyl sulfide, ethyl sulfide, propyl sulfide, and butyl sulfide. From the viewpoint of developability, methyl sulfide and ethyl sulfide are preferred.

Examples of substituents that the alkyl group in the sulfide alkyl group may have include: methoxy group, ethoxy group, chlorine group, bromo group, fluorine group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl, carboxyl, acrylyl, methacrylyl. From the viewpoint of developability, a hydroxyl group and an oligoethylene glycol group are preferred.

R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted group. The alkyl sulfide group is preferably a hydroxyl group or a carboxyl group, and more preferably a carboxyl group from the viewpoint of developability.

In formula (CIII), t represents an integer from 0 to 5. From the viewpoint of manufacturing ease, t is preferably 0.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CIII), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by formula (CIII) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, and particularly preferably 8 mol%. Mol% or more, and preferably 50 Mol% or less, more preferably 40 Mol% or less, further preferably 30 Mol% or less, particularly preferably 20 Mol% or less. By setting the value above the lower limit, heat resistance tends to be improved and a decrease in brightness is suppressed. By setting the value below the upper limit, the content ratio of other partial structures increases, thereby tending to improve alkali solubility. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (CIII) in (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferably 1 to 50 mol%, more preferably 2 to 40 mol%. %, more preferably 5 to 30 mol %, particularly preferably 8 to 20 mol %.

In the case where (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the formula (CI), the other contained partial structures have the following from the viewpoint of developability It is also preferable to describe the partial structure represented by the general formula (CIV).

[Chemistry 20]

In formula (CIV), R ⁷ represents a hydrogen atom or a methyl group.

When (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the formula (CIV), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by the formula (CIV) is not particularly limited, but it is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and more preferably It is 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less. By setting it as above the said lower limit value, alkali solubility tends to improve, and by setting it as below the said upper limit value, there exists a tendency for the storage stability of a colored resin composition to improve. The above upper and lower limits can be combined arbitrarily. For example, (c1) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, the content ratio of the partial structure represented by the formula (CIV) is preferably 5 to 80 mol %, more preferably 10 to 70 mol %. mol%, and more preferably 20 to 60 mol%.

(C) The acid value of the alkali-soluble resin is not particularly limited, but it is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, further preferably 40 mgKOH/g or more, still more preferably 50 mgKOH/g. Above, preferably 60 mgKOH/g or more, more preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, still more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less , especially preferably below 100 mgKOH/g. By setting it as above the said lower limit value, alkali solubility tends to improve, and by setting it as below the said upper limit value, there exists a tendency for the storage stability and substrate adhesion of a colored resin composition to improve. The above upper and lower limits can be combined arbitrarily. For example, the acid value of (C) the alkali-soluble resin is preferably 10 to 300 mgKOH/g, more preferably 30 to 300 mgKOH/g, further preferably 40 to 250 mgKOH/g, still more preferably 50 to 200 mgKOH /g, especially 60-150 mgKOH/g.

(C) The weight average molecular weight of the alkali-soluble resin is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, further preferably 4,000 or more, still more preferably 6,000 or more, still more preferably 7,000 or more, especially preferably It is 8,000 or more, and preferably it is 30,000 or less, more preferably 20,000 or less, further preferably 15,000 or less, especially 10,000 or less. When the value is equal to or higher than the above-mentioned lower limit, heat resistance or coating film hardenability tends to be improved, and when the value is below the above-mentioned upper limit, alkali solubility tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the weight average molecular weight of (C) the alkali-soluble resin is preferably 1,000 to 30,000, more preferably 2,000 to 30,000, further preferably 4,000 to 20,000, still more preferably 6,000 to 20,000, further preferably 7,000 to 15,000. The best value is 8,000 to 10,000.

The content ratio of (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but it is preferably 5 mass % or more, and more preferably 10 mass % or more in the total solid content of the colored resin composition. , more preferably 20 mass% or more, still more preferably 30 mass% or more, especially 40 mass% or more, and more preferably 80 mass% or less, more preferably 70 mass% or less, still more preferably 60 mass% mass% or less, preferably 50 mass% or less. By setting the value above the lower limit, the curability of the coating film during ultraviolet exposure tends to be improved, and by setting the value below the upper limit, the solubility of the developer increases and residues tend to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of (C) alkali-soluble resin in the colored resin composition is preferably 5 to 80 mass %, more preferably 10 to 80 mass %, and still more preferably 5 to 80 mass % of the total solid content of the colored resin composition. 20 to 70 mass%, more preferably 30 to 60 mass%, particularly preferably 40 to 50 mass%.

[1-4] (D) Photopolymerization initiator The colored resin composition of the present invention contains (D) photopolymerization initiator. By containing (D) the photopolymerization initiator, curability can be imparted to the film by photopolymerization. (D) The photopolymerization initiator can also be used as a mixture (photopolymerization initiator system) with an accelerator (chain transfer agent) and optionally added additives such as a sensitizing dye. The photopolymerization starting system is a component with the following functions: directly absorbing light or causing decomposition reaction or hydrogen abstraction reaction through photosensitization to generate polymerization active free radicals.

Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in Japanese Patent Application Laid-Open No. Sho 59-152396 and Japanese Patent Laid-Open No. Sho 61-151197, or Japanese Patent Application Laid-Open No. Sho 61-151197. N-aryl-α-amino acids, N-aryl-alpha-amino acids such as hexaarylbimidazole derivatives, halomethyl-trisene derivatives, and N-phenylglycine described in Japanese Patent Application Laid-Open No. 10-39503 Radical active agents such as hydroxy-α-amino acid salts and N-aryl-α-amino acid esters, and α-amine alkylphenone compounds are described in Japanese Patent Laid-Open No. 2000-80068 Oxime ester starter.

The following are examples of photopolymerization initiators that can be used in the present invention. 2-(4-Methoxyphenyl)-4,6-bis(trichloromethyl)-mesotriene, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) )-Mesesine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-meso-tris, 2-(4-ethoxycarbonylnaphthyl)-4,6 - Bis(trichloromethyl)-s-tris-tris and other halomethylated tris-s derivatives;

2-Trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl) Vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuranyl)vinyl)]-1,3,4 -Halomethylated 㗁adiazole derivatives such as 㗁oxadiazole and 2-trichloromethyl-5-furyl-1,3,4-㗁adiazole; 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole Dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer imidazole derivatives such as (4'-methoxyphenyl)-4,5-diphenylimidazole dimer; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone, Michlerone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromodiphenyl Methyl ketone, 2-carboxybenzophenone and other benzophenone derivatives; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxy Cyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecane phenyl)one, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one, 1,1,1-trichloromethyl-(p-butyl Acetophenone derivatives such as basephenyl)ketone; 9-oxosulfide𠮿 , 2-ethyl-9-oxosulfide𠮿 , 2-isopropyl-9-oxosulfide𠮿 , 2-chloro-9-oxosulfide𠮿 , 2,4-dimethyl-9-oxosulfide𠮿 , 2,4-diethyl-9-oxosulfide𠮿 , 2,4-diisopropyl-9-oxysulfide𠮿 Etc. 9-oxysulfur𠮿 derivative;

Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; Acridine derivatives such as 9-phenyl acridine and 9-(p-methoxyphenyl) acridine; 9,10-dimethylbenzophenidate and other benzophine derivatives; Anthrone derivatives such as benzanthrone; dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium diphenyl, dicyclopentadienyl bis-2,3,4,5,6- Pentafluorobenzene-1-yltitanium, dicyclopentadienylbis-2,3,5,6-tetrafluorobenzene-1-yltitanium, dicyclopentadienylbis-2,4,6-trifluoro Benzene-1-yl titanium, dicyclopentadienyl-2,6-difluorobenzen-1-yl titanium, dicyclopentadienyl-2,4-difluorobenzen-1-yl titanium, dimethyl Cyclopentadienylbis-2,3,4,5,6-pentafluorobenzene-1-yltitanium, dimethylcyclopentadienylbis-2,6-difluorobenzene-1-yltitanium, dimethylcyclopentadienylbis-2,6-difluorobenzene-1-yltitanium, Titanium derivatives such as cyclopentadienyl-2,6-difluoro-3-(pyrrol-1-yl)-phenyl-1-yltitanium;

2-Methyl-1[4-(methylthio)phenyl]-2-𠰌linylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌linylbenzene methyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-𠰌linylphenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, 4 -Isoamyl dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl 1,4-dimethylaminobenzoate, 2,5 -Bis(4-diethylaminobenzyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylaminobenzoyl)coumarin ) Chalcones and other α-aminoalkylphenone compounds; 1,2-Octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone, 1-[9-ethyl-6-(2-methyl oxime ester compounds such as benzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime).

From the viewpoint of sensitivity and surface properties, an oxime ester-based compound (oxime ester-based photopolymerization initiator) is preferred. In its structure, oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates free radicals. Therefore, high sensitivity can be obtained with a small amount, and it is stable to thermal reactions. It can design high-performance products with a small amount. Sensitive colored resin composition. In particular, from the viewpoint of light absorption of i-rays (365 nm) of the exposure light source, an oxime ester compound having a carbazole ring which may have a substituent is preferred.

Examples of the oxime ester compound include compounds represented by the following general formula (I-1).

[Chemistry 21]

In formula (I-1), R ^21a represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ^21b represents any substituent containing an aromatic ring or a heteroaromatic ring. R ^22a represents an optionally substituted alkyl group or an optionally substituted aryl group.

The number of carbon atoms in the alkyl group of R ^21a is not particularly limited. From the viewpoint of solubility in a solvent or sensitivity to exposure, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, and more preferably 20 or less. It is preferably 15 or less, more preferably 10 or less, and particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 2 to 5. Examples of the alkyl group include methyl, ethyl, propyl, cyclopentylethyl, and propyl. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amino groups, amide groups, and 4-(2-methoxy-1-methyl)ethoxy groups. -2-Methylphenyl, or N-acetyl-N-acetyloxyamine group. From the viewpoint of ease of synthesis, unsubstituted is preferred.

Examples of the aromatic ring group of R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but from the viewpoint of the solubility of the colored resin composition, it is preferably 5 or more. Moreover, from the viewpoint of developability, 30 or less is preferable, 20 or less is more preferable, 12 or less is further more preferable, and 8 or less is especially preferable. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the aromatic ring group is preferably 5 to 30, more preferably 5 to 20, further preferably 5 to 12, and particularly preferably 5 to 8.

Examples of the aromatic ring group include phenyl, naphthyl, pyridyl, furyl, and fluoryl. From the viewpoint of developability, a phenyl group, a naphthyl group, and a fluoryl group are preferable, and a phenyl group and a fluoryl group are more preferable. Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group, a carboxyl group, a halogen atom, an amino group, a amide group, and an alkyl group. From the viewpoint of developability, a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is more preferred. Examples of the substituent in the optionally substituted alkyl group or the optionally substituted alkoxy group include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group. From the viewpoint of developability, R ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a methyl group.

R ^21b is any substituent containing an aromatic ring or a heteroaromatic ring. From the viewpoint of solubility in solvents or sensitivity to exposure, preferred are carbazolyl groups which may have a substituent, and 9-oxosulfanyl groups which may have a substituent. group, an optionally substituted diphenyl sulfide group, or an optionally substituted fluorenyl group, and a group in which these groups are linked to a carbonyl group. From the viewpoint of light absorption of i-rays (365 nm) of the exposure light source, a carbazolyl group which may have a substituent or a group in which a carbazolyl group which may have a substituent and a carbonyl group are linked together is preferred.

Examples of substituents that the carbazolyl group may have include: alkyl groups having 1 to 10 carbon atoms such as methyl and ethyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy groups and ethoxy groups; F, Halogen atoms such as Cl, Br, and I; hydroxyl groups with 1 to 10 carbon atoms; alkyl ester groups with 1 to 10 carbon atoms; alkoxycarbonyl groups with 1 to 10 carbon atoms; halogenated alkyl groups with 1 to 10 carbon atoms; Aromatic ring group with 4 to 10 carbon atoms; amino group; aminoalkyl group with 1 to 10 carbon atoms; hydroxyl group; nitro group; CN group; optionally substituted aryl group; optionally substituted heteroaromatic group group; optionally substituted thiophenecarboxylic group.

The number of carbon atoms in the alkyl group of R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity to a solvent, it is preferably 2 or more, more preferably 3 or more, and more preferably 20 or less, more preferably 15 or less, more preferably 10 or less, particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, still more preferably 2 to 5, and particularly preferably 3 to 5. Examples of the alkyl group include aceyl, ethyloyl, propyl and butyl groups. Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, halogen atoms, amine groups, and amide groups. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

The number of carbon atoms in the arylide group of R ^22a is not particularly limited. From the viewpoint of solubility or sensitivity to a solvent, it is preferably 7 or more, more preferably 8 or more, and preferably 20 or less, more preferably 20 or less. 15 or less, more preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aryl group is preferably 7 to 20, more preferably 7 to 15, further preferably 7 to 10, and particularly preferably 8 to 10. Examples of the aryl group include benzyl group and naphthoyl group. Examples of the substituent that the aryl group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, a amide group, and an alkyl group. From the viewpoint of ease of synthesis, unsubstituted groups are preferred.

Examples of the compound represented by the formula (I-1) include the following general formula (I-2) or (I-3) from the viewpoint of light absorption of i-rays (365 nm) of the exposure light source. the compound represented.

[Chemistry 22]

[Chemistry 23]

In formula (I-2) and formula (I-3), R ^21a and R ^22a have the same meaning as in formula (I-1). R ^23a represents an alkyl group which may have a substituent. R ^24a represents an alkyl group which may have a substituent, an aryl group which may have a substituent, a heteroaryl group which may have a substituent, or a nitro group. The benzene ring constituting the carbazole ring can further be condensed with the aromatic ring to form a polycyclic aromatic ring.

The number of carbon atoms in the alkyl group of R ^23a is not particularly limited. From the viewpoint of solubility in a solvent, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less. Furthermore, it is more preferable that it is 10 or less, and it is especially preferable that it is 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 2 to 5. Examples of the alkyl group include methyl, ethyl, propyl, butyl, and cyclohexyl. Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, unsubstituted is preferred. R ^23a is more preferably an ethyl group from the viewpoint of solubility in a solvent and ease of synthesis.

The number of carbon atoms in the alkyl group of R ^24a is not particularly limited. From the viewpoint of solubility in a solvent, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less. Furthermore, it is more preferable that it is 10 or less, and it is especially preferable that it is 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, still more preferably 1 to 5, and particularly preferably 2 to 5. Examples of the alkyl group include methyl, ethyl, propyl, butyl, and cyclohexyl. Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, unsubstituted is preferred.

The number of carbon atoms in the arylide group of R ^24a is not particularly limited. From the viewpoint of solubility in a solvent, it is preferably 7 or more, more preferably 8 or more, further preferably 9 or more, and further preferably 20. or less, more preferably 15 or less, still more preferably 10 or less, particularly preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the carbon number of the aryl group is preferably 7 to 20, more preferably 8 to 15, further preferably 9 to 10, and particularly preferably 9. Examples of the aryl group include benzyl group and naphthoyl group. Examples of the substituent that the aryl group may have include a carbonyl group, a carboxyl group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, ethyl is preferred.

The number of carbon atoms in the heteroaromatic group of R ^24a is not particularly limited. From the viewpoint of solubility in a solvent, it is preferably 7 or more, more preferably 8 or more, further preferably 9 or more, and more preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, especially 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the heteroaromatic group is preferably 7 to 20, more preferably 8 to 15, further preferably 9 to 10, and particularly preferably 9. Examples of the heteroaryl group include benzyl, fluorobenzyl, chlorobenzyl, bromobenzyl, fluoronaphthyl, chloronaphthyl, and bromonaphthyl. . Examples of substituents that the heteroaryl group may have include: carbonyl group, carboxyl group, hydroxyl group, phenyl group, benzyl group, cyclohexyl group, and nitro group. From the viewpoint of ease of synthesis, unsubstituted is preferred. From the viewpoint of sensitivity, R ^24a is preferably an arylyl group which may have a substituent, and more preferably a benzyl group.

The benzene ring constituting the carbazole ring can further be condensed with the aromatic ring to form a polycyclic aromatic ring.

Commercially available products of the oxime ester compound include, for example, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Qianli Electronic New Materials, and ADEKA. N-1919, NCI-930, NCI-831.

Specific examples of the oxime ester compound include the following compounds.

[Chemistry 24]

[Chemical 25]

[Chemical 26]

One type of these photopolymerization initiators may be used alone, or two or more types may be used in combination.

In addition to (D) the photopolymerization initiator, a chain transfer agent can be further used. The so-called chain transfer agent refers to a compound with the following functions: receiving the generated free radicals and transferring the received free radicals to other compounds. As the chain transfer agent, as long as it is a compound with the above-mentioned functions, various chain transfer agents can be used. For example, a mercapto group-containing compound or carbon tetrachloride can be used. When a mercapto group-containing compound is used, there is a chain transfer effect. Higher tendency, therefore better. The reason is believed to be that the S-H bonding energy is small, which easily causes bond breaking and hydrogen abstraction reaction or chain transfer reaction. Effective for improving sensitivity or surface hardening.

Examples of the mercapto group-containing compound include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoethazole, 3-mercapto-1,2,4-triazole, 2-mercapto- 4(3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other mercapto-containing compounds with aromatic rings; hexanedithiol, decanedithiol, butanediol bis(3 -Mercaptopropionate), butylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptopropionate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate) ester), trimethylolpropane trimercaptoacetate, trihydroxyethyl trithiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butylene glycol bis (3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris (3-Mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-tris Ketones and other aliphatic sulfhydryl group-containing compounds. From the viewpoint of surface smoothness, a compound having a plurality of mercapto groups is preferred.

As the mercapto group-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and as the aliphatic mercapto group-containing compound, trimethylolpropane tris(3- Mercaptopropionate), Pentaerythritol Tetrakis (3-Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Trimethylolpropane Tris (3-Mercaptobutyrate), Pentaerythritol Tetrakis (3-Mercaptobutanate) acid ester), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H, 3H,5H)-Triketone.

In terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, and trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), and pentaerythritol tris are preferred. (3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3, 5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6(1H,3H,5H)-trione, preferably pentaerythritol tetrakis(3-mercaptopropionic acid) ester), pentaerythritol tetrakis (3-mercaptobutyrate). One type of these chain transfer agents may be used alone, or two or more types may be used in combination.

In the colored resin composition of the present invention, the content ratio of (D) photopolymerization initiator is not particularly limited, but it is preferably 0.5 mass % or more, more preferably 0.8 in the total solid content of the colored resin composition. Mass % or more, more preferably 1 mass % or more, especially 1.2 mass % or more, and 10 mass % or less, more preferably 8 mass % or less, still more preferably 6 mass % or less, particularly preferably It is 4 mass% or less. When the value is equal to or higher than the above-mentioned lower limit, the curability of the coating film tends to be improved, and when the value is equal to or below the above-mentioned upper limit, visible light absorption tends to be reduced, thereby improving brightness. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content ratio of (D) photopolymerization initiator is preferably 0.5 to 10 mass %, more preferably 0.8 to 8 mass %, based on the total solid content of the colored resin composition. The content is preferably 1 to 6% by mass, and particularly preferably 1.2 to 4% by mass.

When the colored resin composition of the present invention contains a chain transfer agent, the content ratio is not particularly limited, but it is preferably 0.1 mass % or more, and more preferably 0.2 mass % in the total solid content of the colored resin composition. More preferably, it is 0.3% by mass or more, particularly preferably 0.4% by mass or more. Furthermore, it is preferably 3% by mass or less, more preferably 2.5% by mass or less, further preferably 2% by mass or less, especially 1.5%. mass% or less. By setting the value to be not less than the above-mentioned lower limit, solvent resistance tends to be improved, and by being below the above-mentioned upper limit, storage stability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a chain transfer agent, the content ratio is preferably 0.1 to 3% by mass, more preferably 0.2 to 2.5% by mass, and even more preferably in the total solid content of the colored resin composition. It is 0.3-2 mass %, especially 0.4-1.5 mass %.

[1-5] (E) Photopolymerizable monomer The colored resin composition of the present invention contains (E) photopolymerizable monomer. (E) The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but is preferably an addition-polymerizable compound having at least one vinyl double bond (hereinafter referred to as "ethylenic compound"). ). The vinyl compound refers to a compound having an vinyl double bond that undergoes addition polymerization by the action of a photopolymerization initiator and is cured when the colored resin composition of the present invention is irradiated with active light. Furthermore, the monomer in the present invention refers to a concept relative to a so-called polymer substance, and refers to a concept that includes dimers, trimers, and oligomers in addition to monomers in a narrow sense. (E) The photopolymerizable monomer is particularly preferably a polyfunctional vinyl monomer having two or more vinyl double bonds per molecule. The number of ethylenic double bonds of the polyfunctional vinyl monomer is not particularly limited, but it is preferably 2 or more, more preferably 4 or more, further preferably 5 or more, and more preferably 8 or less, It is better to have less than 7. By setting the value above the lower limit, the sensitivity tends to be high, and by setting the value below the upper limit, the solubility in the solvent tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of ethylenic double bonds of the polyfunctional vinyl monomer is preferably 2 to 8, more preferably 2 to 7, further preferably 4 to 7, and particularly preferably 5 to 7.

Examples of the vinyl compound include unsaturated carboxylic acid, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids. Esters, esters obtained by the esterification reaction of unsaturated carboxylic acids and polycarboxylic acids and polyhydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, polyisocyanate compounds and (meth)acrylyl groups A vinyl compound with a urethane skeleton formed by the reaction of a hydroxyl compound.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylates such as acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glyceryl acrylate, etc. Another example is: methacrylate in which the acrylic acid part of the acrylic acid ester is replaced by the methacrylic acid part, itaconic acid ester in which the itaconic acid part is replaced, crotonic acid ester in which the crotonic acid part is replaced, or Maleate ester that replaces the maleic acid moiety.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, and resorcin dimethacrylate. Methacrylate, pyrogallol triacrylate. The ester obtained by the esterification reaction of unsaturated carboxylic acid, polycarboxylic acid and polyhydric hydroxyl compound does not have to be a single substance and can also be a mixture. Examples include: the condensate of acrylic acid, phthalic acid and ethylene glycol, the condensate of acrylic acid, maleic acid and diethylene glycol, the condensate of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid , the condensate of adipic acid, butylene glycol and glycerin.

Examples of the vinyl compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acrylyl group-containing hydroxy compound include hexamethylene diisocyanate and trimethylhexamethylene. aliphatic diisocyanates such as methyl diisocyanate; alicyclic diisocyanates such as cyclohexane diisocyanate and isophorone diisocyanate; aromatic diisocyanates such as toluene diisocyanate and diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate , 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloxymethyl)propane, 3-hydroxy(1,1,1-trimethylacryloxymethyl) Reactant of hydroxyl compounds containing (meth)acrylyl groups such as propane.

Examples of the vinyl compound used in the present invention include acrylamides such as ethyl bisacrylamide; allyl esters such as diallyl phthalate; Vinyl ester and other vinyl-containing compounds. The vinyl compound may be a monomer having an acid value. The monomer having an acid value is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and has an acid group obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound. The multifunctional monomer among the esters is particularly preferably a multifunctional monomer in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol.

One type of these monomers may be used alone. However, since it is difficult to use a single compound in production, two or more types may be used in mixture. Moreover, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used together as monomers. The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, especially 5 to 30 mgKOH/g. By setting the value above the above lower limit, there is a tendency that the development and dissolution characteristics can be improved. By setting the value below the above upper limit, manufacturing or handling can be improved, and photopolymerization performance, surface smoothness of the pixel, etc. can be improved. The hardening tendency tends to be good. Therefore, when two or more polyfunctional monomers with different acid groups are used together, or when a polyfunctional monomer without an acid group is used together, it is preferable to adjust the acid group of the entire polyfunctional monomer to within the above range.

In the present invention, a more preferred polyfunctional monosystem having an acid group is the succinate ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate, which is commercially available as TO1382 manufactured by Toagosei Co., Ltd. A mixture of main ingredients. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. In addition, the polyfunctional monomer described in paragraph [0056] or [0057] of Japanese Patent Application Laid-Open No. 2013-140346 can also be used.

In the present invention, from the viewpoint of improving the chemical resistance of the pixel or the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195971. From the viewpoint of balancing the sensitivity of the coating film and shortening the development time, it is preferable to use the polymerizable monomer described in Japanese Patent Application Laid-Open No. 2013-195974.

In the colored resin composition of the present invention, the content ratio of (E) photopolymerizable monomer is not particularly limited, but it is preferably more than 0 mass %, and more preferably 5 mass % in the total solid content of the colored resin composition. Above, more preferably 10 mass% or more, still more preferably 15 mass% or more, especially 20 mass% or more, and more preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass % or less, more preferably 40 mass % or less, still more preferably 30 mass % or less. By setting it as above the said lower limit value, the curability of a coating film tends to become high, and by setting it as below the said upper limit value, there exists a tendency to suppress the fall of alkali developability. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the (E) photopolymerizable monomer in the colored resin composition is preferably more than 0 mass % and 70 mass % or less, more preferably 5 to 60 mass % in the total solid content of the colored resin composition. % by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, particularly preferably 20 to 30% by mass.

[1-6] Other solid components If necessary, solid components other than the above-mentioned components may be blended into the colored resin composition of the present invention. Examples of such components include dispersants, dispersion aids, surfactants, and adhesion improving agents.

[1-6-1] Dispersant and dispersing aid When the colored resin composition of the present invention contains a pigment as the colorant (A), in order to stably disperse the pigment, it is preferred to contain a dispersing agent. Among dispersants, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, and polyoxyethylene glycol diester dispersants. , Sorbitan aliphatic ester dispersant, aliphatic modified polyester dispersant. Examples of polymer dispersants include the following trade names: EFKA (registered trademark, manufactured by BASF Co., Ltd.), DisperBYK (registered trademark, manufactured by BYK-Chemie Co., Ltd.), Disparlon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark) Trademarks: Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and dispersants described in Japanese Patent Application Laid-Open No. 2013-119568.

As a polymer dispersant, from the viewpoint of dispersibility or storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer having a functional group containing a nitrogen atom is more preferred. things. The block copolymer having a functional group containing a nitrogen atom is preferably composed of an A block having a quaternary ammonium salt group and/or an amine group in the side chain and a B block having no quaternary ammonium salt group or amine group. Segmented A-B block copolymers and B-A-B block copolymers.

Examples of the functional group containing a nitrogen atom include primary to tertiary amino groups and quaternary ammonium salt groups. From the viewpoint of dispersibility or storage stability, primary to tertiary amino groups are preferred, and tertiary amino groups are more preferred. The structure of the repeating unit having a tertiary amine group in the block copolymer is not particularly limited. From the viewpoint of dispersibility or storage stability, a repeating unit represented by the following general formula (d1) is preferred.

[Chemical 27]

In formula (d1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ¹ and R ² may be bonded to each other. Knot to form a ring structure. R ³ is a hydrogen atom or methyl group. X is a 2-valent linking base.

The carbon number of the optionally substituted alkyl group of R ¹ and R ² in formula (d1) is not particularly limited, but is preferably 1 or more, more preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less. For example, 1 to 10 are preferred, 1 to 6 are more preferred, and 1 to 4 are still more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Preferred are methyl, ethyl, propyl, butyl, pentyl and hexyl, more preferred are methyl, ethyl, propyl and butyl. The alkyl group may be either linear or branched. The alkyl group may contain a cyclic structure such as cyclohexyl and cyclohexylmethyl.

The carbon number of the optionally substituted aryl group of R ¹ and R ² in formula (d1) is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 8 the following. For example, 6 to 16 are preferred, 6 to 12 are more preferred, and 6 to 8 are still more preferred. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Preferred are phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferred are phenyl, methylphenyl, and ethylphenyl.

The carbon number of the optionally substituted aralkyl group of R ¹ and R ² in formula (d1) is not particularly limited, but is preferably 7 or more, more preferably 16 or less, more preferably 12 or less, and still more preferably is 9 or less. For example, 7 to 16 are preferred, 7 to 12 are more preferred, and 7 to 9 are still more preferred. Examples of the aralkyl group include phenylmethylene, phenylethylidene, phenylpropylene, phenylbutylene, and phenylisopropylene. Preferred are phenylmethylene, phenylethylidene, phenylpropyl, and phenylbutylene, and more preferred are phenylmethylene and phenylethylidene.

From the viewpoint of dispersibility, storage stability, electrical reliability, and developability, R ¹ and R ² are each independently preferably an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

Examples of substituents that the alkyl group, aralkyl group, and aryl group in the formula (d1) may have include a halogen atom, an alkoxy group, a benzyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, unsubstituted is preferred.

In the formula (d1), examples of the cyclic structure formed by bonding R ¹ and R ² to each other include: a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensation of these two. . The nitrogen-containing heterocyclic ring is preferably not aromatic, and is more preferably a saturated ring. Specific examples include the cyclic structure of the following (IV).

[Chemical 28]

These cyclic structures may further have substituents.

^{In the} formula (d1), examples of the divalent linking group - group [where R ¹³ and R ¹⁴ are a single bond, an alkylene group with 1 to 10 carbon atoms or an ether group (alkoxyalkyl group with 2 to 10 carbon atoms)], preferably -COO-R ¹⁴ - base.

The content ratio of the repeating units represented by formula (d1) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or above, more preferably 15 mol% or more, further preferably 20 mol% or more, especially 25 mol% or more, and more preferably 90 mol% or less, more preferably 70 mol% or less , more preferably 50 mol% or less, particularly preferably 40 mol% or less. Within the above range, there is a tendency to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the repeating units represented by formula (d1) in all the repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and still more preferably 10 to 70 mol%, more preferably 15 to 70 mol%, further preferably 20 to 50 mol%, particularly preferably 25 to 40 mol%.

The block copolymer preferably has a repeating unit represented by the following general formula (d2) from the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and improving the dispersion stability.

[Chemical 29]

In the formula (d2), R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an alkyl group which may have a substituent, and R ¹² is a hydrogen atom or a methyl group. n is an integer from 1 to 20.

The carbon number of the optionally substituted alkyl group of R ¹¹ in formula (d2) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 6 or less, and further Preferably it is 4 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and particularly preferably 2 to 4. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Preferred are methyl, ethyl, propyl, butyl, pentyl and hexyl, more preferred are methyl, ethyl, propyl and butyl. The alkyl group may be either linear or branched. The alkyl group may contain a cyclic structure such as cyclohexyl and cyclohexylmethyl. Examples of substituents that the alkyl group may have include a halogen atom, an alkoxy group, a benzyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, unsubstituted is preferred.

Regarding n in formula (d2), from the viewpoint of compatibility and dispersibility with binder components such as solvents, it is preferably 1 or more, more preferably 2 or more, and more preferably 20 or less, more preferably 10 or less, more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, n is preferably 1 to 10, more preferably 2 to 5.

The content ratio of the repeating units represented by formula (d2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 4 mol% As above, it is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. Within the above range, there is a tendency to achieve both compatibility with binder components such as solvents and dispersion stability. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the repeating units represented by formula (d2) in all the repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4~10 mol%.

The block copolymer preferably has a repeating unit represented by the following general formula (d3) from the viewpoint of improving the compatibility of the dispersant with binder components such as solvents and improving the dispersion stability.

[Chemical 30]

In formula (d3), R ⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ⁹ is a hydrogen atom or a methyl group.

The carbon number of the optionally substituted alkyl group of R ⁸ in formula (d3) is not particularly limited, but is preferably 1 or more, more preferably 10 or less, and more preferably 6 or less. For example, 1 to 10 are preferable, and 1 to 6 are more preferable. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Preferred are methyl, ethyl, propyl, butyl, pentyl and hexyl, more preferred are methyl, ethyl, propyl and butyl. The alkyl group may be either linear or branched. The alkyl group may contain a cyclic structure such as cyclohexyl and cyclohexylmethyl.

The carbon number of the aryl group which may have a substituent in R ⁸ of formula (d3) is not particularly limited, but is preferably 6 or more, more preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 are preferred, and 6 to 12 are more preferred. Examples of the aryl group include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl. Preferred are phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl, and more preferred are phenyl, methylphenyl, and ethylphenyl.

The number of carbon atoms of the optionally substituted aralkyl group of R ⁸ in formula (d3) is not particularly limited, but is preferably 7 or more, more preferably 16 or less, and more preferably 12 or less. For example, 7 to 16 are preferred, and 7 to 12 are more preferred. Examples of the aralkyl group include phenylmethylene, phenylethylidene, phenylpropylene, phenylbutylene, and phenylisopropylene. Preferred are phenylmethylene, phenylethylidene, phenylpropyl, and phenylbutylene, and more preferred are phenylmethylene and phenylethylidene.

From the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group. Examples of substituents that the alkyl group of R ⁸ may have include a halogen atom and an alkoxy group. Examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group. The chain alkyl group represented by R ⁸ includes both linear and branched chains.

The content ratio of the repeating units represented by formula (d3) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% The above ratio is preferably 80 mol% or less, and more preferably 70 mol% or less. Within the above range, there is a tendency to achieve both dispersion stability and high brightness. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the repeating units represented by formula (d3) in all the repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and still more preferably 50~70 mol%.

The block copolymer may have repeating units other than the repeating unit represented by formula (d1), the repeating unit represented by formula (d2), or the repeating unit represented by formula (d3). Examples of such repeating units include: styrene-based monomers derived from styrene and α-methylstyrene; (meth)acrylyl chloride-based monomers such as (meth)acrylyl chloride; (meth)acrylamide monomers such as acrylamide, N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methyl The repeating unit of acryloyl 𠰌line.

From the viewpoint of further improving dispersion, a block copolymer having an A block having a repeating unit represented by formula (d1) and a B block having no repeating unit represented by formula (d1) is preferred. The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. The B block more preferably has a repeating unit represented by formula (d2) and/or a repeating unit represented by formula (d3).

The A block may contain repeating units other than the repeating unit represented by formula (d1). Examples of such repeating units include repeating units derived from the above-mentioned (meth)acrylates. The content of repeating units other than the repeating unit represented by formula (d1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and still more preferably 0 mol%.

The B block may contain a repeating unit represented by the formula (d2) and a repeating unit other than the repeating unit represented by the formula (d3). Examples of such repeating units include: styrene-based monomers derived from styrene and α-methylstyrene; (meth)acrylyl chloride-based monomers such as (meth)acrylyl chloride; (meth)acrylamide monomers such as acrylamide, N-hydroxymethylacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methyl The repeating unit of acryloyl 𠰌line. The content of the repeating unit represented by the formula (d2) and the repeating unit other than the repeating unit represented by the formula (d3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. More preferably, it is 0 mol%.

The acid value of the block copolymer is preferably low in terms of dispersibility, and particularly preferably 0 mgKOH/g. The acid value here refers to the number of milligrams (mg) of KOH required to neutralize 1 g of the solid component of the dispersant.

The amine value of the block copolymer is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more, from the viewpoint of dispersibility and developability. It is preferably 90 mgKOH/g or more, further preferably 100 mgKOH/g or more, particularly preferably 105 mgKOH/g or more. Furthermore, it is preferably 150 mgKOH/g or less, more preferably 130 mgKOH/g or less. The above upper and lower limits can be combined arbitrarily. For example, 30 to 150 mgKOH/g is preferred, 50 to 150 mgKOH/g is more preferred, 70 to 150 mgKOH/g is more preferred, 90 to 130 mgKOH/g is more preferred, and 100 to 100 mgKOH/g is more preferred. 130 mgKOH/g, preferably 105~130 mgKOH/g. The amine value here refers to the amine value converted from the effective solid content, and is a value expressed by the mass of KOH equivalent to the amount of alkali per 1 g of the solid content of the dispersant.

The weight average molecular weight of the block copolymer is preferably 1,000 to 30,000. When the coating is within the above range, the dispersion stability becomes good, and dry foreign matter tends to be less likely to be generated during coating by the slit nozzle method.

The block copolymer can be produced by a known method. For example, it can be produced by living polymerization of monomers introduced into each of the above-mentioned repeating units. As the living polymerization method, for example, Japanese Patent Laid-Open No. 9-62002, Japanese Patent Laid-Open No. 2002-31713, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601(1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977(1985), K. Hatada, K. Ute, et al, Polym . J. 18, 1037(1986), Righthand Koichi, Hatada Koichi, Polymer Processing, 36, 366(1987), Higashimura Toshinobu, Sawamoto Mitsuo, Polymer Papers, 46, 189(1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737(1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300(1985), D. Y. Sogoh, W. R. Hertler et al, Macromolecules, 20, 1473( 1987).

When the colored resin composition of the present invention contains a dispersant, the content ratio of the dispersant is not particularly limited, but it is preferably 0.001 mass % or more, more preferably 0.01 mass % in the total solid content of the colored resin composition. % or more, more preferably 0.1 mass % or more, still more preferably 1 mass % or more, especially 2 mass % or more, and preferably 25 mass % or less, more preferably 20 mass % or less, still more preferably It is 15 mass % or less, especially 10 mass % or less. By setting it as above the said lower limit value, the dispersibility or storage stability tends to improve, and by setting it as below the said upper limit value, there exists a tendency for electrical reliability or developability to improve. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a dispersant, the content ratio of the dispersant in the total solid content of the colored resin composition is preferably 0.001 to 25 mass %, more preferably 0.01 to 25 mass %, and still more preferably Preferably, it is 0.1-20 mass %, More preferably, it is 1-15 mass %, Most preferably, it is 2-10 mass %.

When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant to the pigment is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts per 100 parts by mass of the pigment. Parts by mass or more, more preferably 10 parts by mass or more, more preferably 15 parts by mass or more, especially 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less, still more Preferably, it is 40 parts by mass or less, and more preferably, it is 30 parts by mass or less. By setting it within the above range, a colored resin composition having excellent dispersion stability and high brightness tends to be obtained. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a pigment and a dispersant, the content ratio of the dispersant relative to 100 parts by mass of the pigment is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 50 parts by mass, more preferably 15 to 40 parts by mass, even more preferably 20 to 30 parts by mass.

When the colored resin composition of the present invention contains a pigment, in order to improve the dispersibility of the pigment and improve the dispersion stability, for example, a pigment derivative may be included as a dispersion aid. Specific examples of the pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinphthalone-based, isoindolinone-based, and isoindoline-based , Derivatives of diketopyrrolide, anthraquinone, indanthrene, perylene, pyrenone, diketopyrrolopyrrole, and diketopyrroline pigments. Examples of the substituent of the pigment derivative include: sulfonic acid group, sulfonamide group and its quaternary salt, phthalamide imidemethyl group, dialkylaminoalkyl group, hydroxyl group, carboxyl group, hydroxyl group, and hydroxyl group. The amine group is bonded to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc., preferably a sulfonamide group and its quaternary salt, or a sulfonic acid group, and more preferably a sulfonic acid group. In addition, these substituents may be substituted in plural on one pigment skeleton, or may be a mixture of compounds with different numbers of substitutions. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, and anthracenes Sulfonic acid derivatives of quinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, sulfonic acid derivatives of dimethacin pigments, etc.

[1-6-2] Surfactant The colored resin composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used. In terms of having a low possibility of adversely affecting various properties, nonionic surfactants are preferred. When the colored resin composition of the present invention contains a surfactant, the content ratio of the surfactant is not particularly limited. In the total solid content of the colored resin composition, it is used within the following range: preferably 0.001 mass % or more, more preferably 0.01 mass% or more, further preferably 0.05 mass% or more, especially 0.1 mass% or more, and preferably 10 mass% or less, more preferably 1 mass% or less, still more preferably 0.5% by mass or less, preferably 0.3% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the surfactant in the total solid content of the colored resin composition is preferably 0.001 to 10 mass %, more preferably 0.01 to 1 mass %, still more preferably 0.05 to 0.5 mass %, and particularly preferably It is 0.1~0.3% by mass.

[1-6-3] Adhesion improving agent In order to improve the adhesion with the substrate, the colored resin composition of the present invention may contain an adhesion improving agent. Examples of the adhesive improving agent include silane coupling agents and titanium coupling agents. Silane coupling agent is preferred. Examples of the silane coupling agent include: KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shin-Etsu Silicones Co., Ltd.), Z-6040, Z-6043, Z-6062 (manufactured by Dow Corning Toray Co., Ltd.). One type of silane coupling agent may be used alone, or two or more types may be used in combination. The colored resin composition of the present invention may contain an adhesive improving agent other than a silane coupling agent. Examples include: phosphoric acid-based sealing enhancers and other sealing enhancers.

As the phosphoric acid-based adhesion improving agent, phosphate esters containing (meth)acryloxy groups are preferred. Preferred are phosphoric acid-based adhesion-enhancing agents represented by the following general formulas (g1), (g2), and (g3).

[Chemical 31]

In formulas (g1), (g2), and (g3), R ⁵¹ each independently represents a hydrogen atom or a methyl group. l and l' are each independently an integer from 1 to 10, and m independently represents 1, 2 or 3. Examples of other adhesive improving agents include TEGO (registered trademark) Add Bond LTH (manufactured by Evonik Corporation). These phosphoric acid-based sealing agents or other sealing agents can be used alone, or two can be used in combination.

When the colored resin composition of the present invention contains a close contact improving agent, the content ratio is not particularly limited, but it is preferably 0.1 mass % or more, and more preferably 0.2 mass % or more in the total solid content of the colored resin composition. , more preferably 0.3 mass% or more, particularly preferably 0.4 mass% or more, more preferably 3 mass% or less, more preferably 2 mass% or less, further preferably 1.5 mass% or less, especially 1 mass% %the following. By setting the value above the lower limit, patterning characteristics tend to be improved and pattern adhesion under high-humidity conditions is improved, and by setting the value below the upper limit, generation of residues tends to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains an adhesion improving agent, the content ratio of the total solid content is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and still more preferably 0.3 to 1.5% by mass. %, preferably 0.4 to 1% by mass.

[2] Preparation of colored resin composition Next, the method of preparing the colored resin composition of the present invention will be described.

When preparing a colored resin composition containing a pigment as the colorant (A), first, predetermined amounts of the pigment, solvent and dispersant are respectively weighed, and in the dispersion treatment step, the colorant containing the pigment is dispersed to prepare the pigment. Dispersions. In the dispersion treatment step, for example, a paint conditioner, a sand mill, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, etc. can be used. By performing this dispersion treatment, the colorant is finely divided, so the coating characteristics of the colored resin composition are improved, and the transmittance of the pixels of the color filter substrate of the product is improved.

When dispersing the pigment, as mentioned above, it is preferable to appropriately use a dispersing aid and the like in combination. When using a sand mill for dispersion treatment, it is better to use glass beads or zirconia beads with a diameter of 0.1 to several millimeters. The temperature during the dispersion treatment is set to the following range: preferably 0°C or higher, more preferably room temperature or higher, and preferably 100°C or lower, more preferably 80°C or lower. Furthermore, regarding the dispersion time, the appropriate time varies depending on the composition of the pigment dispersion and the size of the sand mill, so it can be adjusted appropriately.

A solvent, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable monomer, and if necessary components other than the above are mixed with the pigment dispersion liquid obtained by the dispersion treatment to prepare a uniform dispersion solution. Furthermore, in each step of the dispersion treatment and mixing, fine dirt may be mixed in, so it is preferable to filter the obtained pigment dispersion through a filter or the like.

When a pigment is not included as the colorant (A), a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable monomer, and other components other than the above if necessary may be mixed to form a uniform solution. obtained in its form. It is preferable to filter the obtained solution through a filter or the like.

[3] Production of hardened material and color filter The hardened material of the present invention is obtained by hardening the colored resin composition of the present invention. Furthermore, the color filter of the present invention has pixels produced using the colored resin composition of the present invention. Below, an example of a manufacturing method of a color filter is explained.

[3-1] Substrate (Support) As the substrate to which the colored resin composition of the present invention is applied, a transparent substrate is preferred, and its material is not particularly limited as long as it is transparent and has appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, and thermoplastic resins such as polycarbonate, polymethylmethacrylate, and polyurethane. Sheets, thermosetting resin sheets such as epoxy resin, unsaturated polyester resin, poly(meth)acrylic resin, or various glasses. Among them, from the viewpoint of heat resistance, glass or heat-resistant resin is preferred.

In order to improve surface physical properties such as adhesion, the substrate coated with the colored resin composition and the substrate provided with the following black matrix may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, urethane resin, etc., if necessary. Film forming processing of various resins, etc. The thickness of the substrate is preferably 0.05 mm or more, more preferably 0.1 mm or more, and preferably 10 mm or less, more preferably 7 mm or less. For example, 0.05 to 10 mm is preferred, and 0.1 to 7 mm is more preferred. In addition, when performing thin film formation processing of various resins, the film thickness is preferably 0.01 μm or more, more preferably 0.05 μm or more, and preferably 10 μm or less, more preferably 5 μm or less. For example, 0.01 to 10 μm is preferred, and 0.05 to 5 μm is more preferred.

[3-2] Black matrix formation step: A black matrix is provided on a transparent substrate to form red, green, and blue pixel images, whereby the color filter of the present invention can be manufactured. The colored resin composition of the present invention is preferably used as a coating liquid for forming green pixels (photoresist patterns) among red, green, and blue pixels. Use a green pixel (photoresist pattern) forming coating liquid to coat the surface of the resin black matrix formed on the transparent substrate, or the surface of the metal black matrix formed using other light-shielding metal materials such as chromium compounds. , heating and drying, image exposure, development and baking processes to form a pixel image.

The black matrix is formed on the substrate using a light-shielding metal film or a colored resin composition for black matrix. As the light-shielding metal material, for example, metal chromium, chromium compounds such as chromium oxide and chromium nitride, nickel and tungsten alloys may be used, and the materials may be laminated in a plurality of layers. Metal light-shielding films are usually formed by sputtering. After forming the desired pattern in a film shape using a positive photoresist, an etching solution mixed with ceric ammonium nitrate and perchloric acid and/or nitric acid is used to chromium. Other materials are etched using an etching solution suitable for the material, and finally the positive photoresist is stripped off with a special stripper to form a black matrix.

When a light-shielding metal film is used, a thin film of these metals or metal-metal oxides is first formed on a transparent substrate by evaporation or sputtering. Then, after forming a coating film of the colored resin composition on the film, a photomask having a repeating pattern such as stripes, mosaics, triangles, etc. is used to expose and develop the coating film to form a photoresist pattern. Thereafter, the coating film is etched to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a black matrix is formed using a colored resin composition containing a black colorant. For example, one or a plurality of black colorants including carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc. can be used, or red, green, and green pigments suitably selected from inorganic or organic pigments and dyes can be used. A black matrix is formed from a colored resin composition containing a black color material mixed with blue and the like in the same manner as the method for forming red, green, and blue pixels described below.

[3-3] Pixel forming step The pixel forming step of forming a pixel includes: a coating step of applying the above-mentioned colored resin composition on a substrate, and a pre-baking step of pre-baking the coating film obtained in the above-mentioned coating step. Baking steps. In the pixel formation step, for example, through a coating step of applying a colored resin composition of one color among red, green, and blue on a substrate provided with a black matrix, the obtained coating film is dried (prebaked). ), a photomask is stacked on the coating film, and an image exposure step is performed through the photomask. In the development step, thermal hardening or photohardening is performed as necessary, thereby forming pixels. A color filter image can be formed by performing these steps on three colored resin compositions of red, green, and blue respectively. The colored resin composition of the present invention is preferably used as a composition for forming green or blue pixels (photoresist patterns) among red, green, and blue pixels, and more preferably is used as a composition for forming green pixels. And use. For example, a green or blue pixel (photoresist pattern) forming composition is used on a resin black matrix formation surface formed on a substrate, or a metal black matrix formation surface is formed using other light-shielding metal materials such as chromium compounds. Each process of coating, drying (prebaking), image exposure, development, and thermal hardening or photohardening is performed to form pixels.

[3-4] Coating step: The colored resin composition can be coated on the substrate by, for example, spin coating, wire bar coating, flow coating, die coating, roller coating, or spray coating. Proceed according to law. Among them, if the die coating method is used, the amount of the colored resin composition used can be greatly reduced, and the influence of the mist (mist) that adheres when using the spin coating method is completely eliminated, and the generation of foreign matter can be suppressed, etc. Better from a comprehensive point of view.

Regarding the thickness of the coating film, if it is too large, it may become difficult to develop the pattern and adjust the gap in the liquid crystal unitization step. On the other hand, if it is too small, it may be difficult to increase the pigment concentration and the desired expression may not be achieved. The color of hope. The thickness of the coating film is preferably 0.2 μm or more, more preferably 0.5 μm or more, further preferably 0.8 μm or more, based on the film thickness after drying, and preferably 20 μm or less, more preferably 10 μm or less. , and more preferably 5 μm or less. For example, 0.2 to 20 μm is preferred, 0.5 to 10 μm is more preferred, and 0.8 to 5 μm is still more preferred.

[3-5] Pre-baking step The drying (pre-baking) of the coating film obtained in the coating step is preferably by using a drying method using a heating plate, IR (Infrared, infrared) oven or convection oven. After predrying, it is preferable to perform prebaking for reheating. The conditions for pre-drying can be appropriately selected based on the types of the above-mentioned solvent components, the performance of the dryer used, etc. The drying temperature and drying time are selected based on the type of solvent components, the performance of the dryer used, etc. Specifically, the drying temperature is preferably 40°C or higher, more preferably 50°C or higher, and more preferably 80°C. or less, more preferably 70°C or less, and the drying time is preferably 15 seconds or more, more preferably 30 seconds or more, and further, preferably 5 minutes or less, more preferably 3 minutes or less.

The temperature condition of pre-baking is preferably higher than the pre-drying temperature. In the present invention, it is specifically 80°C or higher, preferably 90°C or higher, especially 100°C or higher, and preferably 200°C or lower, more preferably 160°C or lower, especially 130°C or lower. When the value is above the lower limit, the dissolution rate tends to become faster. When the value is below the upper limit, the binder resin decomposes and thermal polymerization is induced, resulting in poor development. The above-mentioned upper limit and lower limit can be combined arbitrarily. For example, the pre-baking temperature is preferably 80 to 200°C, more preferably 90 to 130°C, and particularly preferably 100 to 130°C.

The drying time of pre-baking also depends on the heating temperature, and is preferably 10 seconds or more, more preferably 15 seconds or more, and is preferably 10 minutes or less, more preferably 5 minutes or less.

[3-6] Exposure step In the pixel formation step, it is preferable to have an exposure step after the pre-baking step. The exposure step is performed as follows: a negative matrix pattern is stacked on the coating film obtained through the pre-baking step, and a light source of ultraviolet or visible light is irradiated through the mask pattern. At this time, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, if necessary, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer and then exposed. The light source used in the above exposure is not particularly limited. Examples of the light source include light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, or argon ions. Laser, YAG (Yttrium Aluminum Garnet) laser, excimer laser, nitrogen laser, helium-cadmium laser, semiconductor laser and other laser light sources. When used by irradiating light of a specific wavelength, an optical filter can also be used.

[3-7] Development step In the pixel formation step, it is preferable to have a development step after the exposure step. It can be produced by exposing a coating film using the colored resin composition of the present invention in the above-mentioned exposure step and then developing it using an aqueous solution containing a surfactant and an alkaline compound, and Form an image on the substrate. The aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, and phosphoric acid. Inorganic alkaline compounds such as sodium, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, or monoethanolamine, diethanolamine or triethanolamine, monomethylamine, dimethylamine or Trimethylamine, monoethylamine, diethylamine or triethylamine, monoisopropylamine or diisopropylamine, n-butylamine, monoisopropanolamine, diisopropanolamine or triisopropanolamine, ethyleneimine , ethylenediimide, tetramethylammonium hydroxide (TMAH), choline and other organic alkaline compounds. One type of these basic compounds may be used alone, or two or more types may be used in combination.

Examples of surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Anionic surfactants such as nonionic surfactants, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinate salts, etc. agents, alkyl betaines, amino acids and other amphoteric surfactants.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents can be used together with aqueous solutions. The conditions for development are not particularly limited. The development temperature is preferably 10°C or higher, more preferably 15°C or higher, further preferably 20°C or higher, and preferably 50°C or lower, more preferably 45°C or lower, and further preferably 45°C or lower. The best temperature is below 40℃. For example, 10 to 50°C is preferred, 15 to 45°C is more preferred, and 20 to 40°C is still more preferred. As the development method, any method such as a immersion development method, a jet development method, a brush development method, or an ultrasonic development method can be used.

[3-7] Thermal hardening treatment step In the pixel forming step, it is also preferable to have a heat hardening treatment step after the development step. As for the thermal hardening treatment conditions in the thermal hardening treatment step, the temperature is preferably 100°C or higher, more preferably 150°C or higher, and the temperature is preferably 280°C or lower, more preferably 250°C or lower, and the time is preferably 5 minutes or longer. , and preferably 60 minutes or less.

After the above pixel forming steps, patterned pixels of one color are formed. This step is repeated in sequence to pattern black, red, green, and blue, thereby creating a color filter. Furthermore, the order of patterning of the four colors is not limited to the above order.

[3-8] Formation of transparent electrodes The color filter of the present invention can form transparent electrodes such as ITO (Indium Tin Oxides) directly on the image, and can be used as part of components of color displays, liquid crystal display devices, etc. , but in order to improve surface smoothness or durability, top coatings such as polyamide and polyimide can also be provided on the image if necessary. In addition, in some applications such as planar alignment type driving method (IPS mode), transparent electrodes may not be formed.

[4] Image display device (panel) The image display device of the present invention has a color filter produced by the manufacturing method of the present invention. In the following, as image display devices, liquid crystal display devices and organic EL display devices will be described in detail.

[4-1] Liquid crystal display device The manufacturing method of the liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention is usually manufactured in the following manner: an alignment film is formed on the color filter produced by the manufacturing method of the present invention, spacers are spread on the alignment film, and a counter substrate is bonded to form a liquid crystal cell. , inject liquid crystal into the formed liquid crystal cell and connect it to the counter electrode. The alignment film is preferably a resin film such as polyimide. The alignment film is usually formed by gravure printing and/or flexographic printing, and the thickness of the alignment film is tens of nanometers. After hardening the alignment film by thermal baking, surface treatment is performed by irradiation with ultraviolet rays or treatment with a rubbing cloth to achieve a surface state that can adjust the slope of the liquid crystal.

The spacer is preferably a spacer having a size corresponding to the gap (gap) between the opposing substrates, and is usually preferably 2 to 8 μm. A photosensitive spacer (PS) of a transparent resin film can also be formed on the color filter substrate by photolithography and used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (Thin Film Transistor) substrate is particularly preferred.

The bonding gap with the counter substrate varies depending on the use of the liquid crystal display device, but is preferably selected within the range of 2 μm to 8 μm. After being bonded to the counter substrate, parts other than the liquid crystal injection port are sealed with sealing materials such as epoxy resin. The sealing material is hardened by UV (ultraviolet, ultraviolet) irradiation and/or heating, thereby sealing the periphery of the liquid crystal cell. After the liquid crystal unit with a sealed periphery is cut into panel units, the pressure is reduced in a vacuum chamber. After the liquid crystal injection port is immersed in liquid crystal, the liquid crystal is injected into the liquid crystal unit by leaking into the chamber. The degree of pressure reduction in the liquid crystal cell is preferably 1×10 ^-2 Pa or less, more preferably 1×10 ^-3 Pa or less, and more preferably 1×10 ^-7 Pa or more, more preferably 1×10 ^-6 The range is above Pa. For example, 1×10 ^-7 to 1×10 ^-2 Pa is preferred, and 1×10 ^-6 to 1×10 ^-3 Pa is more preferred. Moreover, it is preferable to heat the liquid crystal cell during decompression, and the heating temperature is preferably 30°C or higher, more preferably 50°C or higher, and preferably 100°C or lower, more preferably 90°C or lower. For example, 30 to 100°C is preferred, and 50 to 90°C is more preferred.

It is preferable to maintain the temperature during decompression in the range of not less than 10 minutes and not more than 60 minutes, and then immerse it in the liquid crystal. The UV curable resin is cured and the liquid crystal injection port of the liquid crystal unit into which liquid crystal is injected is sealed, thereby completing a liquid crystal display device (panel). The type of liquid crystal is not particularly limited and can be any of previously known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, such as lyotropic liquid crystal, thermotropic liquid crystal, and the like. Known thermotropic liquid crystals include nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like, and any of them may be used.

[4-2] Organic EL display device When producing an organic EL display device having a color filter produced by the manufacturing method of the present invention, for example, as shown in Figure 1, the organic EL display device formed by the present invention is formed on a transparent support substrate 10. The colored resin composition is used to form a blue color filter with pixels 20, and the organic light-emitting body 500 is laminated on the blue color filter through the organic protective layer 30 and the inorganic oxide film 40, thereby producing a variety of colors. Organic EL element.

An example of a lamination method of the organic light-emitting body 500 is: sequentially forming the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light-emitting layer 53, the electron injection layer 54 and the cathode 55 on the upper surface of the color filter. method; or a method of bonding the organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40, etc. The organic EL device 100 fabricated in this way can be applied to a passively driven organic EL display device or an actively driven organic EL display device. [Example]

Next, although an Example and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to the following Example as long as it does not deviate from the summary.

<Phthalocyanine compound A> Phthalocyanine compound A having the following chemical structure, which was synthesized based on Example 30 of Japanese Patent Application Laid-Open No. 05-345861, was used.

[Chemical 32]

Furthermore, Et in the formula represents an ethyl group.

<Phthalocyanine compound B>

[Chemical 33]

<Dispersant A> A methacrylic AB block copolymer containing an A block having a functional group containing a nitrogen atom and a B block having a solvophilic group. Having a repeating unit represented by the following formula (1a), a repeating unit represented by the following formula (2a), a repeating unit represented by the following formula (3a), a repeating unit represented by the following formula (4a), and A repeating unit represented by the following formula (5a). The amine value is 120 mgKOH/g and the acid value is less than 1 mgKOH/g.

The content ratios of repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a) among all repeating units are less than 1 mol%, 34.5 mol%, and less, respectively. 6.9 mol%, 13.8 mol%, and 6.9 mol%.

[Chemical 34]

<Alkali-soluble resin A> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing it with nitrogen, and the temperature was raised to 120°C. 10 parts by mass of styrene, 85 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and then heated at 120°C. Continue stirring for 2 hours. Next, the reaction vessel was replaced with air, 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 43 parts by mass of acrylic acid, and the reaction was continued at 120° C. for 6 hours. Thereafter, 20 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120° C. for 3.5 hours. The alkali-soluble resin A thus obtained had a weight average molecular weight Mw measured by GPC in terms of polystyrene of about 8000, an acid value of 30 mgKOH/g, and a double bond equivalent of 410 g/mol.

<Alkali-soluble resin B> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing it with nitrogen, and the temperature was raised to 120°C. 5 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate and 4 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and then heated at 120°C Continue stirring for 2 hours. Next, the reaction vessel was replaced with air, 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 67 parts by mass of acrylic acid, and the reaction was continued at 120° C. for 6 hours. Thereafter, 15 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120° C. for 3.5 hours. The alkali-soluble resin B thus obtained had a weight average molecular weight Mw measured by GPC in terms of polystyrene of about 9000, an acid value of 24 mgKOH/g, and a double bond equivalent of 260 g/mol.

<Alkali-soluble resin C> 145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing it with nitrogen, and the temperature was raised to 120°C. 7 parts by mass of styrene, 92 parts by mass of glycidyl methacrylate, and 62 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and then heated at 120°C. Continue stirring for 2 hours. Next, the reaction vessel was replaced with air, 0.7 parts by mass of tris(dimethylaminomethyl)phenol and 0.12 parts by mass of hydroquinone were added to 47 parts by mass of acrylic acid, and the reaction was continued at 120° C. for 6 hours. Thereafter, 39 parts by mass of succinic anhydride and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 120° C. for 3.5 hours. The alkali-soluble resin C thus obtained had a weight average molecular weight Mw measured by GPC in terms of polystyrene of about 5700, an acid value of 89 mgKOH/g, and a double bond equivalent of 430 g/mol.

Among the alkali-soluble resins A to C, the alkali-soluble resin C with an acid value of 89 mgKOH/g has the highest solubility. Regarding the alkali-soluble resin A and the alkali-soluble resin B which have the same level of lower acid value, the alkali-soluble resin B containing more glycidyl methacrylate with higher hydrophilicity has higher solubility.

<Alkali-soluble resin D> Prepare a detachable flask equipped with a condenser tube as a reaction tank, add 400 parts by mass of propylene glycol monomethyl ether acetate, replace it with nitrogen, and heat it with an oil bath while stirring to increase the temperature of the reaction tank. Raise temperature to 90°C.

On the other hand, 30 parts by mass of 2,2'-[oxybis(methylene)]bis-2-acrylic acid dimethyl ester, 60 parts by mass of methacrylic acid, and cyclohexyl methacrylate were added to the monomer tank. 110 parts by mass, 5.2 parts by mass of tert-butylperoxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate. Add 5.2 parts by mass of n-dodecanethiol and 5.2 parts by mass of propylene glycol monomethyl ether to the chain transfer agent tank. After stabilizing the temperature of the reaction tank at 90°C, 27 parts by mass of methyl ether acetate was added dropwise from the monomer tank and the chain transfer agent tank to start polymerization. While maintaining the temperature at 90°C, dropwise addition was performed over 135 minutes each, and 60 minutes after the completion of the dropwise addition, the temperature was started to rise so that the reaction tank reached 110°C.

After maintaining the temperature at 110° C. for 3 hours, a gas introduction pipe was installed in the separable flask, and oxygen/nitrogen = 5/95 (v/v) mixed gas was started to be introduced. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts by mass of triethylamine were added to the reaction tank. , react directly at 110°C for 9 hours. After cooling to room temperature, an alkali-soluble resin D was obtained with a polystyrene-converted weight average molecular weight Mw measured by GPC of 9000, an acid value of 101 mgKOH/g, and a double bond equivalent of 550 g/mol.

<Preparation of green dye dispersion A> As described in Table 1, 9.9 parts by mass of phthalocyanine compound A, 0.1 parts by mass of dispersant A in terms of solid content, and 72.0 parts by mass of propylene glycol monomethyl ether as a solvent were prepared Acetate (including the solvent derived from dispersant A), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container, and dispersed for 6 hours with a paint shaker. . After the dispersion is completed, the beads and the dispersion liquid are separated by a filter, thereby preparing a green dye dispersion liquid A.

<Preparation of green dye dispersion B> Green dye dispersion B was prepared in the same manner as green dye dispersion A, except that phthalocyanine compound A was changed to phthalocyanine compound B and each raw material was prepared as described in Table 1. .

<Preparation of Yellow Pigment Dispersion A> As described in Table 1, 11.4 parts by mass of C.I. Pigment Yellow 138, 2.9 parts by mass of dispersant A in terms of solid content, and 5.7 parts by mass of alkali in terms of solid content were prepared. Soluble resin D, 76.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (also including the solvent derived from dispersant A and the solvent derived from alkali-soluble resin D), 4.0 parts by mass of propylene glycol monomethyl ether, 225 parts by mass Fill a stainless steel container with zirconia beads with a diameter of 0.5 mm, and use a paint shaker to disperse them for 6 hours. After the dispersion is completed, the beads and the dispersion liquid are separated by a filter, thereby preparing a yellow pigment dispersion liquid A.

[Table 1] Green dye dispersion A Green dye dispersion B Yellow pigment dispersion A Allocation ratio green dye Phthalocyanine compound A 9.9 Phthalocyanine compound B 9.0 yellow pigment CI Pigment Yellow 138 11.4 Dispersant (solid content conversion) Dispersant A 0.1 1.0 2.9 Dispersion resin (solid content conversion) Alkali soluble resin D 5.7 Solvent Propylene glycol monomethyl ether acetate 72.0 72.0 76.0 Propylene glycol monomethyl ether 18.0 18.0 4.0

<Photopolymerizable Monomer A> Pentaerythritol tetraacrylate (Light acrylate PE-4A, manufactured by Kyoeisha Chemical Co., Ltd.)

<Photopolymerizable Monomer B> Polyethoxylated tetramethylolmethane tetraacrylate (NK ESTER ATM-4E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Photopolymerization Initiator A> An oxime ester compound with the following chemical structure (4-Acetyloxyimino-5-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-5-pentoxyvalerate methyl ester )

[Chemical 35]

Furthermore, Me in the formula represents a methyl group.

＜Surfactant A＞ MEGAFAC F-554 (manufactured by DIC Corporation)

<Preparation of Colored Resin Composition> Each component described in Table 2 was mixed at the stated solid content ratio to prepare colored resin compositions 1 to 8. Furthermore, in the colored resin compositions 1 to 8, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether ( PGME) as the solvent, the mixing ratio (mass ratio) of PGMEA/PGME in the obtained colored resin composition was 90/10.

[Table 2] Colored resin composition 1 2 3 4 5 6 7 8 Mixing ratio (solid content) Green dye dispersion A 24.0 16.6 14.2 27.5 22.6 20.4 Green dye dispersion B 21.3 30.2 Yellow pigment dispersion A 14.5 26.6 49.0 8.4 22.6 20.8 22.5 8.4 Alkali soluble resin A 32.8 35.4 26.1 30.1 27.5 32.7 Alkali soluble resin B 38.5 12.0 Alkali soluble resin C 5.1 Photopolymerizable monomer A 24.6 15.4 24.6 24.6 24.6 24.6 24.6 Photopolymerizable monomer B 15.6 Photopolymerization initiator A 4.0 2.9 4.0 4.0 4.0 4.0 4.0 4.0 Surfactant A 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

<Evaluation of spectral change> The obtained colored resin composition was coated on a 50 mm square, 0.7 mm thick glass substrate by the spin coating method so that the film thickness after thermal hardening treatment (baking) became 2.0 μm. (manufactured by AGC, AN100), dried under reduced pressure, and then pre-baked on a hot plate at the temperature listed in Table 3 for 90 seconds to prepare a colored substrate. In addition, after drying under reduced pressure in the same method, prebaking was not performed, but thermal hardening treatment was performed at 230° C. for 20 minutes in a clean oven to produce a baked colored substrate.

For the obtained colored substrate and the baked colored substrate, a spectrophotometer U-3310 manufactured by Hitachi Manufacturing Co., Ltd. was used to measure the spectral transmission spectrum at every 1 nm from the wavelength of 380 nm to 780 nm, and convert it into an absorption spectrum. In the absorption spectrum of the colored substrate, let the absorbance value at wavelength n be A ⁿ , and let the same value of the colored substrate after baking be A ₀ ⁿ . At this time, the following numerical formula is used to define the degree of spectral change as an indicator of how the absorption spectrum of the colored substrate is different from that of the baked colored substrate. The calculated spectral change degree is shown in Table 3. The smaller the degree of spectral change in the following numerical formula, the more it indicates that the phthalocyanine compound (1) forms aggregates during pre-baking and is close to the state after roasting and completely forming aggregates.

[Number 1]

<Evaluation of dissolution rate> Using 0.04 mass% potassium hydroxide aqueous solution, the above-mentioned colored substrate was developed at a developer temperature of 23°C. The time until complete dissolution was measured and is shown in Table 3.

<Evaluation of Adhesion> The obtained colored resin composition was coated by spin coating on a 50 mm square, 0.7 mm thick glass substrate ( Manufactured by AGC Company, AN100), pre-baked at 100°C for 90 seconds. Then, a 2 kW high-pressure mercury lamp was used to perform exposure processing at an exposure dose of 40 mJ/cm ² and an illumination intensity of 30 mW/cm ² through an exposure mask having a plurality of linear openings with a width of 1 to 50 μm. Thereafter, a 0.04% by mass potassium hydroxide aqueous solution was used and a development process was performed for 60 seconds at a developer temperature of 23°C. Then, spray water washing treatment was carried out for 10 seconds under the water pressure of 1 kg/ ^cm2 . Thereafter, thermal hardening treatment was performed at 230° C. for 20 minutes to produce a pattern substrate. Using an optical microscope, observe the pattern corresponding to a plurality of linear openings with a width of 1 to 50 μm. When the width of the narrowest opening of the remaining pattern that has not disappeared during development is 7 μm or less, it is rated A. When it exceeds 7 μm and is not more than 15 μm, it is rated B. When it exceeds 15 μm, it is rated B. C. The evaluation results are shown in Table 3 and Table 4. The narrower the width of the opening, the better the adhesion between the cured product of the colored resin composition and the substrate.

<Evaluation of Contrast> The obtained colored resin composition was coated on a 50 mm square, 0.7 mm thick glass substrate (AGC) by the spin coating method so that the film thickness after thermal hardening treatment (baking) became 2.0 μm. Manufactured by the company, AN100), pre-baked at 100°C for 90 seconds. Then, the exposure process was performed using a 2 kW high-pressure mercury lamp at an exposure dose of 40 mJ/cm ² and an illumination intensity of 30 mW/cm ² , and a thermal hardening process was performed at 230°C for 20 minutes to prepare a substrate for contrast evaluation. Using a contrast tester CT-1 (manufactured by TSUBOSAKA ELECTRIC Co., Ltd.), the obtained substrate was measured for orthogonal parallelism, and the contrast ratio (1:12000) was determined based on parallelism/orthogonality. Those with a contrast ratio of 6,000 or more are classified as A, those with a contrast ratio of 4,000 or more but less than 26,000 are classified as B, and those with a contrast ratio of less than 4,000 are classified as C. The evaluation results are shown in Table 4.

<Evaluation of Residue> A pattern substrate was produced in the same manner as for the adhesion evaluation, and the pattern corresponding to the linear opening with a width of 50 μm was observed using an optical microscope. When no residue is observed in the opening, the rating is A. When some residue is observed in the opening but there is no practical problem, it is rated B. When residue is observed in the opening, the rating is C. The evaluation results are shown in Table 4.

[table 3] composition (A) Content ratio (mass %) of phthalocyanine compound A in the colorant Tightness Pre-baking temperature (℃) 105 100 90 80 Example 1 Colored resin composition 1 74 A Spectral variability 9 10 12 18 Dissolution speed (seconds) twenty four twenty four twenty four 28 Comparative example 1 Colored resin composition 2 52 B Spectral variability 12 13 20 31 Dissolution speed (seconds) 12 12 15 20 Comparative example 2 Colored resin composition 3 33 B Spectral variability 32 36 65 77 Dissolution speed (seconds) 31 37 102 >200

[Table 4] composition (A) Content ratio (mass %) of phthalocyanine compound A in the colorant (A) Content ratio (mass %) of phthalocyanine compound B in the colorant Tightness Contrast residue Example 1 Colored resin composition 1 74 A A A Comparative example 1 Colored resin composition 2 52 B C B Comparative example 2 Colored resin composition 3 33 B C B Example 2 Colored resin composition 4 85 A A A Example 3 Colored resin composition 5 70 A A A Comparative example 3 Colored resin composition 6 63 B B B Comparative example 4 Colored resin composition 7 60 A B B Comparative example 5 Colored resin composition 8 85 A B B

It is clear from Table 3 that as the content ratio of the phthalocyanine compound (1) in the colorant (A) increases, the degree of spectral change when the prebaking temperature is low becomes smaller. In other words, the higher the content ratio of the phthalocyanine compound (1) in the colorant (A), the lower the required prebaking temperature is because the phthalocyanine compound (1) forms aggregates. Especially in Comparative Example 2, when the prebaking temperature is 105°C, the value of the spectral change degree is also slightly larger, indicating that the phthalocyanine compound (1) does not completely form aggregates. This is thought to be because the colorant (A) contains a colorant other than the phthalocyanine compound (1), which causes π-π stacking of the aromatic rings contained in its structure, thereby preventing the phthalocyanine compounds (1) from interacting with each other. gather. In addition, the dissolution rate also shows the same trend. As the content ratio of the phthalocyanine compound (1) in the colorant (A) becomes higher, the dissolution rate becomes fixed at the prebaking temperature when the prebaking temperature gradually increases from 80°C. Low. This is thought to be because the phthalocyanine compound (1) forms an aggregate, and therefore the (C) alkali-soluble resin contained in the colored resin composition is wound around it to form a complex, which is separate from the phthalocyanine compound (1). Compared with the previous situation, the dissolution rate becomes faster. By making the dissolution speed of the colored resin composition faster, the development time can be shortened. In addition, the dissolution speed can be accelerated at a lower pre-baking temperature, which can help improve the production efficiency of color filters. Furthermore, it is thought that by making the dissolution rate faster, the solubility of (C) the alkali-soluble resin can be relatively reduced, so that the pattern is less likely to peel off during development and the adhesion is improved.

From the comparison between Examples 1 to 3 and Comparative Examples 1 to 3 in Table 4, it is clear that: (A) When the content ratio of the phthalocyanine compound (1) in the colorant is 65 mass % or more, the residue and contrast are greatly improved. . The reason for this is considered to be that by increasing the content ratio of the phthalocyanine compound (1), the aggregation of the phthalocyanine compounds (1) is less likely to be hindered by other colorants, and regular aggregates of the phthalocyanine compound (1) are formed. formation, the contrast becomes high, and the dissolution rate becomes faster due to the formation of regular aggregates of the phthalocyanine compound (1). Furthermore, it is clear from Comparative Examples 4 and 5 in Table 4 that when a phthalocyanine compound B that is not a phthalocyanine compound (1) is used, regardless of the content ratio of the phthalocyanine compound B in the colorant (A), Residue and poor contrast. It is thought that compared with fluorine atoms, chlorine atoms occupy a larger volume, and the formation of regular aggregates of phthalocyanine compounds is hindered, resulting in a failure to improve contrast and dissolution rate.

Although the present invention has been described in detail using specific aspects, it is understood by those skilled in the art that various modifications and changes can be made without departing from the intention and scope of the present invention.

10:Transparent support substrate 20: pixels 30: Organic protective layer 40: Inorganic oxide film 50:Transparent anode 51: Hole injection layer 52: Hole transport layer 53: Luminous layer 54:Electron injection layer 55:Cathode 100: Organic EL element 500: Organic luminophore

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL (Electroluminescence) element having a color filter of the present invention.

Claims (13)

A colored resin composition, characterized in that it contains (A) colorant, (B) solvent, (C) alkali-soluble resin, (D) photopolymerization initiator, and (E) photopolymerizable monomer , and the above-mentioned (A) colorant contains a phthalocyanine compound having a chemical structure represented by the following general formula (1) and a yellow colorant, and the content ratio of the above-mentioned phthalocyanine compound in the above-mentioned (A) colorant is 65 mass % More than 90% by mass; [Chemical 1] (In formula (1), A ¹ to A ¹⁶ each independently represents a hydrogen atom, a halogen atom or a group represented by the following general formula (2); wherein, at least one of A ¹ to A ¹⁶ represents a fluorine atom, and One or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2)) [Chemical 2] (In formula (2), X represents a divalent linking group; the benzene ring in formula (2) may have any substituent; * represents a bond). The colored resin composition according to claim 1, wherein the content ratio of the phthalocyanine compound in the colorant (A) is 70 mass% or more and 90 mass% or less. The colored resin composition of claim 1 or 2, wherein the halogen atoms of A ¹ to A ¹⁶ in the above formula (1) are fluorine atoms. The colored resin composition according to any one of claims 1 to 3, wherein in the above formula (1), at least one of ^A1 to ^A4 is a fluorine atom, and at least one of ^A5 to ^A8 is a fluorine atom, One or more of A ⁹ to A ¹² is a fluorine atom, and one or more of A ¹³ to A ¹⁶ is a fluorine atom. The colored resin composition according to any one of claims 1 to 4, wherein the benzene ring in the above formula (2) has an alkoxycarbonyl group. The colored resin composition according to any one of claims 1 to 5, wherein X in the above formula (2) is an oxygen atom. The colored resin composition according to any one of claims 1 to 6, wherein in the above formula (1), at least one of A ¹ to A ⁴ is a group represented by the above formula (2), and among A ⁵ to A ⁸ One or more of them is a group represented by the above formula (2), one or more of A ⁹ to A ¹² is a group represented by the above formula (2), and one or more of A ¹³ to A ¹⁶ is a group of the above formula (2) The basis represented. The colored resin composition according to any one of claims 1 to 7, wherein the yellow colorant is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 185 and a nickel azo complex represented by the following formula (i) At least one of the groups; [Chemistry 3] . The colored resin composition of claim 1, wherein the content ratio of the yellow colorant in the colorant (A) is 10 mass% or more and 35 mass% or less. The colored resin composition according to any one of claims 1 to 9, wherein the content ratio of the colorant (A) in the total solid content of the colored resin composition is 10 mass % or more and 80 mass % or less. A hardened product obtained by hardening the colored resin composition according to any one of claims 1 to 10. A color filter provided with pixels produced using the colored resin composition according to any one of claims 1 to 10. An image display device having a color filter as claimed in claim 12.

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