WO2023176888A1

WO2023176888A1 - Color filter manufacturing method and image display device manufacturing method

Info

Publication number: WO2023176888A1
Application number: PCT/JP2023/010090
Authority: WO
Inventors: 紫陽平岡; 宏明石井; 幸治福岡
Original assignee: 三菱ケミカル株式会社
Priority date: 2022-03-16
Filing date: 2023-03-15
Publication date: 2023-09-21
Also published as: CN118843811A; TW202401048A

Abstract

Provided is a color filter manufacturing method having a fast developing-solution dissolution rate and high production efficiency. This color filter manufacturing method according to the present invention is characterized by comprising a pixel formation step in which pixels are formed on a substrate using a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer. The color filter manufacturing method is also characterized in that: the pixel formation step includes a coating step for coating the colored resin composition on the substrate and a prebake step for prebaking the coated film obtained by the coating step; a specific phthalocyanine compound is used as the (A) colorant; the (C) alkali-soluble resin has a hydroxyl group or a carboxy group; and the prebake temperature is 95°C or more.

Description

Method for manufacturing color filter and method for manufacturing image display device

The present invention relates to a method of manufacturing a color filter and a method of manufacturing an image display device. This application claims priority based on Japanese Patent Application No. 2022-040963 filed in Japan on March 16, 2022, the contents of which are incorporated herein.

Conventionally, pigment dispersion methods, dyeing methods, electrodeposition methods, and printing methods are known as methods for manufacturing color filters used in liquid crystal display devices and the like. Among these, the pigment dispersion method, which has excellent properties on average in terms of spectral properties, durability, pattern shape, accuracy, etc., is most widely adopted.

In recent years, color filters are required to have higher brightness, higher contrast, and a wider color gamut. Pigments are generally used as coloring materials to determine the color of color filters from the viewpoint of heat resistance, light resistance, etc. However, pigments are no longer able to meet market demands, especially for high brightness, and color The use of dyes instead of pigments as materials is being actively investigated. For example, studies have been made to use phthalocyanine dyes for green pixel applications (see, for example, Patent Documents 1 to 3).

Japanese Patent Application Publication No. 2019-113732 International Publication No. 2020/171060 Japanese Patent Application Publication No. 2020-046655

The present inventors investigated and found that in the colored resin composition described in Patent Document 1, the solubility in the developer varies depending on the temperature during pre-bake (drying process of the coating film performed before the exposure process). It was found that the dissolution rate in the developer was slow, especially when the pre-bake temperature was in a low temperature range.

Therefore, an object of the present invention is to provide a method for manufacturing a color filter that has a fast developer dissolution rate and high production efficiency.

As a result of intensive studies, the present inventors have discovered that the above-mentioned problems can be solved by setting the pre-bake temperature to a specific temperature or higher, leading to the present invention.
That is, the present invention has the following configuration.

[1] Using a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, A method for manufacturing a color filter, comprising a pixel forming step of forming pixels on the
The pixel forming step includes a coating step of coating the colored resin composition on the substrate, and a pre-baking step of pre-baking the coating film obtained in the coating step,
As the colorant (A), a phthalocyanine compound having a chemical structure represented by the following general formula (1) is used,
The alkali-soluble resin (C) is a resin having a hydroxyl group or a carboxyl group,
A method for manufacturing a color filter, characterized in that the pre-baking temperature is 95°C or higher.

(In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A ¹ to A ¹⁶ represents a fluorine atom.
In addition, one or more of A ¹ to A ⁴ is a group represented by the following general formula (2), and one or more of A ⁵ to A ⁸ is a group represented by the following general formula (2). and one or more of A ⁹ to A ¹² is a group represented by the following general formula (2), and one or more of A ¹³ to A ¹⁶ is a group represented by the following general formula (2). be. )

(In formula (2), X represents a divalent linking group. The benzene ring in formula (2) has a carbonyl group. * represents a bond.)

[2] The method for producing a color filter according to [1], wherein the pre-baking temperature is 100° C. or higher.

[3] The method for producing a color filter according to [1] or [2], wherein the pre-baking temperature is 105° C. or higher.
[4] The method for producing a color filter according to any one of [1] to [3], wherein the pre-baking temperature is 110° C. or higher.

[5] Using a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer, A method for manufacturing a color filter, comprising a pixel forming step of forming pixels on the
The pixel forming step includes a coating step of coating the colored resin composition on the substrate, and a pre-baking step of pre-baking the coating film obtained in the coating step,
As the colorant (A), a phthalocyanine compound having a chemical structure represented by the following general formula (1) is used,
The alkali-soluble resin (C) is a resin having a hydroxyl group or a carboxyl group,
A method for manufacturing a color filter, characterized in that in the prebaking step, the phthalocyanine compound is prebaked so that the spectral change rate is less than 1.0.

[6] A method for manufacturing an image display device, comprising manufacturing an image display device using a color filter manufactured by the manufacturing method according to any one of [1] to [5].

According to the present invention, it is possible to provide a method for manufacturing a color filter that has a fast developer dissolution rate and high production efficiency.

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

In the present invention, the term "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, "total solid content" shall mean all components other than the solvent in the colored resin composition. Even if components other than the solvent are liquid at room temperature, they are not included in the solvent but included in the total solid content.
In the present invention, the "amine value" refers to the amine value in terms of effective solid content unless otherwise specified, and is a value expressed by the amount of base and the mass of KOH equivalent to 1 g of solid content of the dispersant.
In the present invention, "C.I." means color index.

One embodiment of the method for producing a color filter of the present invention includes (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photoinitiator, and (E) a photopolymerizable monomer. A method for manufacturing a color filter comprising a pixel forming step of forming pixels on a substrate using a colored resin composition, the pixel forming step comprising a coating step of applying the colored resin composition on the substrate; A pre-baking step of pre-baking the coating film obtained in the coating step, using a phthalocyanine compound having a chemical structure represented by the following general formula (1) as the (A) colorant, and using the (C) alkali-soluble The resin has a hydroxyl group or a carboxy group, and the prebaking temperature is 95°C or higher.

Another embodiment of the method for producing a color filter of the present invention includes (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photoinitiator, and (E) a photopolymerizable monomer. A method for producing a color filter, comprising a pixel forming step of forming pixels on a substrate using a colored resin composition, the pixel forming step comprising a coating step of applying the colored resin composition onto the substrate. , and a pre-baking step of pre-baking the coating film obtained in the coating step, using a phthalocyanine compound having a chemical structure represented by the following general formula (1) as the (A) colorant, and (C) using a phthalocyanine compound having a chemical structure represented by the following general formula (1). The alkali-soluble resin is a resin having a hydroxyl group or a carboxy group, and the prebaking step is characterized in that the prebaking step is performed such that the spectral change rate of the phthalocyanine compound is less than 1.0.

The colored resin composition of the present invention, the pixel formation process, the coating process of coating the colored resin composition on the substrate included in the pixel formation process, and the prebaking process of prebaking the coating film obtained in the coating process will be described below. .

[1] Colored resin composition The colored resin composition in the present invention includes (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photoinitiator, and (E) a photopolymerizable monomer. including. Furthermore, if necessary, other additives other than the above-mentioned components may be blended.

[1-1] (A) Colorant The (A) colorant contained in the colored resin composition of the present invention is a phthalocyanine compound (hereinafter referred to as "phthalocyanine compound") having a chemical structure represented by the following general formula (1). 1).

In formula (2), X represents a divalent linking group. The benzene ring in formula (2) has a carbonyl group. * represents a bond.

The coloring agent (A) included in the colored resin composition of the present invention includes a phthalocyanine compound (1). When the intermolecular distance of the phthalocyanine compound (1) is shortened by heating, the phthalocyanine compound (1) assembles regularly according to the formula (2) that constitutes the phthalocyanine skeleton, and the carbonyl group protrudes on the outer periphery of the aggregate, resulting in efficient It is thought that the dissolution rate of the phthalocyanine compound (1) in the developer becomes faster because it becomes capable of hydrogen bonding with the alkali-soluble resin.

(A ¹ to A ¹⁶ )
In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by formula (2). However, one or more of A ¹ to A ¹⁶ represents a fluorine atom, one or more of A ¹ to A ⁴ is a group represented by formula (2), and one or more of A ⁵ to A ⁸ is a group represented by formula (2). One or more of them is a group represented by formula (2), one or more of A ⁹ to A ¹² is a group represented by formula (2), and one or more of A ¹³ to A ¹⁶ is a group represented by formula (2). It is a group represented by formula (2).

Examples of the halogen atom in A ¹ to A ¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine atoms are preferred from the viewpoint of high brightness.
One or more of A ¹ to A ¹⁶ is preferably a fluorine atom, more preferably 6 or more fluorine atoms, even more preferably 7 or more, particularly preferably 8 or more, and 15 or more fluorine atoms or less, preferably 12 or less, and more preferably 10 or less. Setting the value above the lower limit tends to improve the stability of the phthalocyanine compound (1), and setting the value below the upper limit improves the affinity with the dispersant and solvent in the colored resin composition. Tend. The above upper and lower limits can be arbitrarily combined. For example, the number of substituents representing fluorine atoms among A ¹ to A ¹⁶ is 1 to 15, preferably 6 to 12, more preferably 7 to 12, and even more preferably 8 to 10.

(X)
X in formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, but includes, for example, an oxygen atom, a sulfur atom, 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 firing, 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) has a carbonyl group.
Examples of carbonyl groups include alkoxycarbonyl groups (-COOR ^A group (where R ^A represents an alkyl group)) and aryloxycarbonyl groups (-COOR ^B group (where R ^B represents an aryl group)). ). From the viewpoint of development solubility and brightness, an alkoxycarbonyl group is preferred.

The alkyl group (R ^A ) contained in the alkoxycarbonyl group (-COOR ^A group) may be linear, branched, or cyclic, but from the viewpoint of affinity with organic solvents, a linear alkyl group is preferred. It is preferable that
The number of carbon atoms in the alkyl group (R ^A ) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. Setting the amount above the lower limit tends to suppress aggregation and suppressing foreign substances, and setting it below the upper limit tends to improve solvent affinity and stability over time. The above upper and lower limits can be arbitrarily combined. For example, the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the alkyl group (R ^A ) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From the viewpoint of inhibiting aggregation, a methyl group or an ethyl group is preferable, and an ethyl group is more preferable. preferable.

The aryl group (R ^B ) included in the aryloxycarbonyl group (-COOR ^B group) may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The number of carbon atoms in the aryl group (R ^B ) is not particularly limited, but is preferably 4 or more, more preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. Setting the amount above the lower limit tends to suppress aggregation due to steric repulsion, and setting the amount below the upper limit tends to improve solvent affinity and stability over time. The above upper and lower limits can be arbitrarily combined; for example, the number of carbon atoms in 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 a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring, each having one free valence.
The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, pyrrole rings, 2H-pyran rings, 4H-thiopyran rings, pyridine rings, 1,3-oxazole rings, and isoxazole rings, each having one free valence. ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo Examples include an imidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a 1,8-naphthyridine ring, a purine ring, and a pteridine ring.

The benzene ring in formula (2) has a carbonyl group, and the number of carbonyl groups is not particularly limited, but the dye molecules stack with each other, improving heat resistance and suppressing a decrease in brightness due to decomposition of the dye. From the viewpoint of this, it is preferable that the number of substitutions per benzene ring is 1.
The benzene ring in formula (2) has a carbonyl group, and the substitution position may be o-position, m-position, or p-position, but from the viewpoint of enabling stacking in a close-packed structure. , p-position is preferred.

One or more of A ¹ to A ¹⁶ represents a fluorine atom, but from the viewpoint of improving brightness by forming an association between two molecules of the phthalocyanine compound (1), one or more of A ¹ to A ⁴ represents a fluorine atom. , one or more of A ⁵ to A ⁸ 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. Preferably; two or more of A ¹ to A ⁴ are fluorine atoms, two or more of A ⁵ to A ⁸ are fluorine atoms, and two or more of A ⁹ to A ¹² are fluorine atoms. It is more preferable that two or more of A ¹³ to A ¹⁶ are fluorine atoms.

In formula (1), one or more of A ¹ to A ⁴ is a group represented by formula (2), and one or more of A ⁵ to A ⁸ is a group represented by formula (2). and one or more of A ⁹ to A ¹² is a group represented by formula (2), and one or more of A ¹³ to A ¹⁶ is a group represented by formula (2) ; Two or more of A ¹ to A ⁴ are groups represented by formula (2), two or more of A ⁵ to A ⁸ are groups represented by formula (2), and A ⁹ to Preferably, two or more of A ¹² are groups represented by formula (2), and two or more of A ¹³ to A ¹⁶ are groups represented by formula (2).
From the viewpoint that luminance reduction is suppressed by efficient stacking, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , 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 preferably halogen atoms; A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , 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 It is particularly preferred that ¹⁶ is a fluorine atom.

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

Note that in the above formula, Et represents an ethyl group.

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

The colorant (A) may contain other colorants in addition to the phthalocyanine compound (1). Other colorants include pigments and dyes. When the colored resin composition of the present invention is used for green pixels, it is preferable to use, for example, a green coloring material such as a green pigment or a green dye, or a yellow coloring material such as a yellow pigment or a yellow dye.
From the viewpoint of color reproducibility required for green pixels, it is preferable that the colorant (A) contains a yellow coloring material in addition to the phthalocyanine compound (1).
Examples of green pigments include C.I. I. Pigment Green 7, 36, 58, 59, 62, and 63, and C. I. Pigment Green 58 is preferred.
Among the green dyes classified as dyes in the color index, C. I. Examples of solvent dyes include C.I. I. Examples include Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35. C. I. Examples of acid dyes include C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C. I. Examples include

Mordant Green

1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, and 53. From the viewpoint of suppressing dye decomposition during thermal firing, C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, and 35 are preferred.

Examples of yellow pigments include C.I. 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 a 1:1 complex of azobarbituric acid with nickel represented by the following formula (i) or a tautomer thereof, and other compounds (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

Other compounds inserted into the nickel azo complex represented by formula (i) include, for example, compounds represented by formula (ii) below.

Among these, from the viewpoint of high brightness and high color gamut, C. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, nickel azo complexes represented by formula (i) are preferred; I. Pigment Yellow 83, 138, 139, 180, 185 and the nickel azo complex represented by formula (i) are more preferred.

Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include compounds described in Japanese Patent Application Publication No. 2010-168531.
Among the yellow dyes classified as dyes in the color index, C. I. Examples of solvent dyes include C.I. I. Examples include Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, and 163. C. I. Examples of acid dyes include C.I. 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 and derivatives thereof. Can be mentioned. C. I. As a direct dye, for example, C.I. 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, and 141 dyes. C. I. As a mordant dye, for example, C.I. I. Examples include

Mordant Yellow

5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 dyes. Preferably 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 and derivatives thereof.
From the viewpoint of suppressing dye decomposition during firing, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 are preferred.

(A) When the colorant contains a yellow coloring material in addition to the phthalocyanine compound (1), the yellow coloring material is C.I. I. Pigment Yellow 138, 185 and the nickel azo complex represented by formula (i) 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 atomizing the pigment, for example, a solvent salt milling method is suitably used.

The content ratio of the colorant (A) in the colored resin composition in the present invention is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass in the total solid content of the colored resin composition. The above is more preferable, even more preferably 25% by mass or more, particularly preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and 40% by mass. The following are particularly preferred. Setting the value above the lower limit value tends to make it possible to reproduce a wide range of hues, and setting the value below the upper limit value tends to ensure stability over time. The above upper and lower limits can be arbitrarily combined. For example, the content of the colorant (A) in the colored resin composition is preferably 10 to 80% by mass, more preferably 15 to 80% by mass, and further preferably 20 to 60% by mass in the total solid content of the colored resin composition. It is preferably 25 to 50% by weight, even more preferably 30 to 40% by weight.

The content ratio of the phthalocyanine compound (1) in the colored resin composition in the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and 5% by mass in the total solid content of the colored resin composition. The above is more preferable, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, also preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and 20% by mass. The following are particularly preferred. Setting the value above the lower limit value tends to improve brightness, and setting the value below the upper limit value tends to ensure stability over time. The above upper and lower limits can be arbitrarily combined. For example, the content of the phthalocyanine compound (1) in the colored resin composition is more preferably 3 to 50% by mass, even more preferably 5 to 50% by mass, and 10 to 40% by mass in the total solid content of the colored resin composition. is even more preferred, and 15 to 30% by mass is particularly preferred.

When the colored resin composition of the present invention contains other colorants, the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the total solid content of the colored resin composition. The content is more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Setting the value above the lower limit value tends to make it possible to reproduce a wide range of hues, and setting the value below the upper limit value tends to ensure stability over time. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains other colorants, the content of the other colorants is preferably 1 to 30% by mass, more preferably 3 to 30% by mass in the total solid content of the colored resin composition. , more preferably 5 to 25% by weight, even more preferably 7 to 25% by weight, particularly preferably 10 to 20% by weight.

[1-2] (B) Solvent In the colored resin composition or pigment dispersion in the present invention, (A) colorant, (C) alkali-soluble resin, (D) photopolymerization initiator, ( E) It has the function of dissolving or dispersing the photopolymerizable monomer and other components and adjusting the viscosity.
(B) Any solvent may be used as long as it can dissolve or disperse each component.

(B) Examples of the solvent 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, propylene glycol mono-n-butyl ether, Propylene glycol-t-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, dipropylene glycol monomethyl ether, 3-methyl - Glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
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, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycol alkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 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, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentanone Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

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, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Etherketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile are mentioned.

Commercially available solvents applicable to the above include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, So Cal Solvent No. 1 and no. 2. Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names). These solvents may be used alone or in combination of two or more.

When forming pixels of a color filter by photolithography, the solvent (B) is a solvent with a boiling point in the range of 100 to 200°C (under a pressure of 1013.25 [hPa]. Hereinafter, all boiling points are the same). It is preferable to select More preferred is a solvent with a boiling point of 120 to 170°C.
Among the above-mentioned solvents, glycol alkyl ether acetates are preferred from the standpoint of having a good balance in coating properties, surface tension, etc., and relatively high solubility of the constituent components in the composition.

Glycol alkyl ether acetates may be used alone, or may be used in combination with other solvents. Particularly preferred solvents used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferred from the viewpoint of solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, which tends to reduce the storage stability such as increasing the viscosity of the colored resin composition obtained later. When glycol monoalkyl ethers are used in combination, the proportion of glycol monoalkyl ethers in the solvent (B) is preferably 5 to 30% by mass, more preferably 5 to 20% by mass.

In another embodiment, a solvent having a boiling point of 150° C. or higher can be used in combination. By using a solvent with a boiling point of 150°C or higher, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult to destroy the mutual relationships among the constituent components in the pigment dispersion due to rapid drying. . When a solvent with a boiling point of 150°C or higher is used in combination, the content of the solvent with a boiling point of 150°C or higher in the solvent (B) is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, Particularly preferred is 5 to 30% by weight. By setting the value above the lower limit, for example, there is a tendency to prevent coloring material components from precipitating and solidifying at the tip of the slit nozzle and causing foreign body defects, and by setting the value below the upper limit, the composition There is a tendency to avoid problems such as slow drying speed and tact failure in the vacuum drying process and pin marks during pre-baking.
The solvent with a boiling point of 150° C. or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, there is no need to separately contain a solvent with a boiling point of 150° C. or higher.
Preferably, the solvent having a boiling point of 150° C. or higher includes, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate. , triacetin.

When forming pixels of a color filter by an inkjet method, suitable solvents (B) have a boiling point of preferably 130°C or more and 300°C or less, more preferably 150°C or more and 280°C or less. By setting it to the lower limit or more, the uniformity of the resulting coating film tends to be better, and by setting it to the upper limit or less, it tends to easily reduce the amount of residual solvent during firing.
The vapor pressure of the solvent used is preferably 10 mmHg or less, more preferably 5 mmHg or less, still more preferably 1 mmHg or less, from the viewpoint of uniformity of the resulting coating film.

When manufacturing color filters using the inkjet method, the ink emitted from the nozzle is very fine, ranging from several to several tens of pL, so the solvent evaporates and the ink condenses and dries before it lands around the nozzle opening or within the pixel bank. It tends to harden. In order to avoid this, it is preferable that the solvent (B) contains a solvent with a high boiling point, and specifically, it is preferable that the solvent (B) contains a solvent with a boiling point of 180° C. or higher. It is more preferable to include a solvent with a boiling point of 200°C or higher, and it is particularly preferable to include a solvent with a boiling point of 220°C or higher. When a solvent with a boiling point of 180°C or higher is included, the content ratio of the solvent with a boiling point of 180°C or higher in the solvent (B) is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. is most preferred. By setting it to the above lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.

Examples of solvents with 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, 1,3-butylene glycol diacetate, 1,6- Examples include hexanol diacetate and triacetin.
A solvent having a boiling point lower than 180° C. may be included in order to adjust the viscosity of the colored resin composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and for example, ethers, esters, and ketones are preferable. Among these, preferred are, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate.

On the other hand, if the solvent contains alcohol, the ejection stability in the inkjet method may deteriorate. When alcohols are used together, the content of alcohol in the solvent (B) is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

The content ratio of the solvent (B) in the colored resin composition in the present invention is not particularly limited, but its upper limit is preferably 99% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. . When the amount is below the upper limit, it tends to be easier to form a coating film. On the other hand, the lower limit of the solvent content is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, taking into account the viscosity suitable for coating. The above upper and lower limits can be arbitrarily combined. For example, the content of the solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and even more preferably 80 to 85% by mass.

[1-3] (C) Alkali-soluble resin The colored resin composition in the present invention contains (C) an alkali-soluble resin, and the (C) alkali-soluble resin is a resin having a hydroxyl group or a carboxy group. By containing the alkali-soluble resin (C), it is possible to achieve both film curability by photopolymerization and solubility by developer.
(C) Alkali-soluble resins include, for example, Japanese Unexamined Patent Application No. 7-207211, Japanese Unexamined Patent Application No. 8-259876, Japanese Unexamined Patent Application No. 10-300922, and Japanese Unexamined Patent Application No. 11-140144. , Japanese Patent Application Publication No. 11-174224, Japanese Publication No. 2000-56118, and Japanese Publication No. 2003-233179 can be used. Among them, the following resins (C-1) to (C-5) are preferred.
(C-1): A copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, in which an unsaturated monobasic acid is added to at least a portion of the epoxy groups in the copolymer. An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction (hereinafter sometimes referred to as "resin (C-1)"). )
(C-2): Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as "resin (C-2)").
(C-3): A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the 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)").
Among these, resin (C-1) is particularly preferred.

Resins (C-2) to (C-5) may be any resin as long as it has solubility to the extent that it can be dissolved in an alkaline developer and the desired development process can be carried out, and each resin is disclosed in Japanese Patent Application Publication No. 2009 The resins described in the same item in Japanese Patent No. 025813 can be preferably employed.

(C-1): A copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, in which an unsaturated monobasic acid is added to at least a portion of the epoxy groups in the copolymer. An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a part of the hydroxyl groups produced by the addition reaction.As one of the preferred embodiments of the resin (C-1), "epoxy group In a copolymer containing 5 to 90 mol% of (meth)acrylate and 10 to 95 mol% of other radically polymerizable monomers, 10 to 100 mol% of the epoxy groups contained in the copolymer are unsaturated. Examples include resins obtained by adding a monobasic acid, or alkali-soluble resins obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction.

Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. An example is acrylate glycidyl ether. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

The other radically polymerizable monomer to be copolymerized with the epoxy group-containing (meth)acrylate is preferably a mono(meth)acrylate having a structure represented by the following general formula (V).

In formula (V), R ⁹¹ to R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Note that R ⁹⁶ and R ⁹⁸ or R ⁹⁵ and R ⁹⁷ may be linked 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, and may be either saturated or unsaturated, and Preferably, the number is 5-6.

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 the 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 colored resin composition can be used to form a color filter. There is a tendency for the intensity of pixels formed to increase.

The mono(meth)acrylates having the structure represented by formula (V) may be used alone or in combination of two or more.

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

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

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

Other radically polymerizable monomers other than the mono(meth)acrylate represented by formula (VI) are not particularly limited, but specific examples include styrene, styrene α-, o- , m-, p-alkyl, nitro, cyano, amide, vinyl aromatics such as ester derivatives; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth)acrylate, (meth) Ethyl acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, (meth)acrylate tert-butyl, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( Dodecyl meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth)acrylic acid Adamantyl, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, piperonyl (meth)acrylate, (meth)acrylate Salicyl acid, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, (meth)acrylate Cresyl acid, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-iso (meth)acrylate -Propyl, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, -2-hydroxyethyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid esters such as 2-hydroxypropyl acrylate; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-diethylamide; (meth)acrylic acid amides such as acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-iso-propylamide, (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide , (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and other vinyl compounds; diethyl citraconate, diethyl maleate, diethyl fumarate , unsaturated dicarboxylic acid diesters such as diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide; N-(meth)acryloyl phthalimide can be mentioned.

Among these other radically polymerizable monomers, styrene, benzyl (meth)acrylate, and monomaleimide are preferred from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition.
If the copolymer of epoxy group-containing (meth)acrylate and other radically polymerizable monomer contains any repeating unit derived from styrene, benzyl (meth)acrylate, or monomaleimide, other radical polymerization Among the repeating units derived from the monomer, the total content of the repeating units derived from styrene, the repeating units derived from benzyl (meth)acrylate, and the repeating units derived from monomaleimide is 1 to 70 mol%. Preferably, 3 to 50 mol% is more preferable.

A known solution polymerization method can be applied to the copolymerization reaction of the 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 solvents used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Alkyl ether acetates; Propylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol ; Triethylene glycol dialkyl ethers; Propylene glycol dialkyl ethers; Dipropylene glycol dialkyl ethers; Ethers such as 1,4-dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Benzene, toluene Hydrocarbons such as , xylene, octane, and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; Lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; Dimethylformamide, N- Examples include methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The amount of the solvent used in the solution polymerization method is preferably 30 to 1000 parts by weight, more preferably 50 to 800 parts by weight, based on 100 parts by weight of the resulting copolymer. By controlling the amount of solvent used within the above range, it tends to become easier to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. . Examples of the organic peroxide catalyst include catalysts classified as known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxy esters, and peroxydicarbonates.

Examples of the radical polymerization initiator used in the copolymerization reaction include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and t-hexyl peroxybenzoate. , t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2 , 5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, Bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butyl peroxide) oxy)3,3,5-trimethylcyclohexane and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.

Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.
Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature.
The amount of the radical polymerization initiator used is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 100 parts by weight of the monomers used in the copolymerization reaction.

The copolymerization reaction may be carried out by dissolving the monomers and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by dissolving the monomers and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring. The monomer may be added dropwise into a heated and stirred solvent, or a radical polymerization initiator may be added to the solvent and the monomer may be added dropwise into the heated solvent.
Reaction conditions can be set depending on the target molecular weight.

In the present invention, the copolymer of epoxy group-containing (meth)acrylate and other radically polymerizable monomers includes 5 to 90 mol% of repeating units derived from epoxy group-containing (meth)acrylate and other radically polymerizable monomers. It is preferable that the repeating unit consists of 10 to 95 mol% of the repeating unit derived from the epoxy group-containing (meth)acrylate and 20 to 80 mol% of the repeating unit originating from the epoxy group-containing (meth)acrylate and another radically polymerizable monomer. More preferably, 80 to 20 mol% of repeating units; 30 to 70 mol% of repeating units derived from epoxy group-containing (meth)acrylate and 70 to 30 mol% of repeating units derived from other radically polymerizable monomers. % is particularly preferred.

By setting the content ratio of repeating units derived from the epoxy group-containing (meth)acrylate to the above-mentioned lower limit or more, the amount of the unsaturated monobasic acid or polybasic acid anhydride to be described later tends to be sufficient.
By setting the content of repeating units derived from other radically polymerizable monomers to the above lower limit or more, heat resistance and strength tend to be sufficient.
Next, unsaturated monobasic acid (polymerizable component) and polybasic acid anhydride (alkali-soluble component) are added to the epoxy group of the copolymer of epoxy group-containing (meth)acrylate and other radically polymerizable monomers. ) to react.

As the unsaturated monobasic acid to be added to the epoxy group, known unsaturated monobasic acids can be used, such as unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Examples of unsaturated monobasic acids to be added to epoxy groups include (meth)acrylic acid; crotonic acid; o-, m-, p-vinylbenzoic acid; or monocarboxylic acids such as (meth)acrylic acid substituted with a cyano group or the like. Among them, (meth)acrylic acid is preferred. These unsaturated monobasic acids may be used alone or in combination of two or more.

By adding an unsaturated monobasic acid to an epoxy group, polymerizability can be imparted to the resin (C-1).
The unsaturated monobasic acid is added to usually 10 to 100 mol%, preferably 30 to 100 mol%, more preferably 50 to 100 mol% of the epoxy groups possessed by the copolymer. By setting it as the above-mentioned lower limit or more, there is a tendency for the stability of the colored resin composition to improve over time.
A known method can be used to add an unsaturated monobasic acid to the epoxy group of the copolymer.

Further, as the polybasic acid anhydride to be 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 dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; trimellitic anhydride; Examples include anhydrides of acids having three or more bases, such as pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

Alkali solubility can be imparted to the resin (C-1) 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.
The polybasic acid anhydride is usually 10 to 100 mol%, preferably 20 to 90 mol%, more preferably 30 to 80 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer. Add to %. By setting it below the above-mentioned upper limit, the residual film rate during development tends to be good, and by setting it above the above-mentioned lower limit, solubility tends to become sufficient.
As a method for adding a polybasic acid anhydride to a hydroxyl group generated by adding an unsaturated monobasic acid to an epoxy group possessed by the copolymer, a known method can be employed.

Furthermore, in order to improve photosensitivity, after adding a polybasic acid anhydride, glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to some of the generated carboxyl groups. good.
In order to improve developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a portion of the generated carboxy groups.

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 glycidyl ether compounds having a phenyl group or an alkyl group.
Commercially available glycidyl ether compounds having no polymerizable unsaturated groups include, for example, Nagase ChemteX's product names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", and "Denacol EX-141". Denacol EX-145,""DenacolEX-146,""DenacolEX-171," and "Denacol EX-192."

The structure of the resin (C-1) is described in, for example, Japanese Patent Application Publication No. 8-297366 and Japanese Patent Application Publication No. 2001-89533.
The weight average molecular weight of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. By setting it above the above-mentioned lower limit, heat resistance and film strength tend to be good, and by setting it below the above-mentioned upper limit, solubility in a developer tends to become good.
As a guideline 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 exposure to ultraviolet rays, among the alkali-soluble resins (C), (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferable.
(c1) The partial structure containing the side chain having an ethylenically unsaturated group in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but the coating film curability upon exposure to ultraviolet rays and alkaline development From the viewpoint of achieving both alkali solubility and alkali solubility, it is preferable to have, for example, a partial structure represented by the following general formula (CI).

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

Furthermore, among the partial structures represented by the formula (CI), the partial structure represented by the following general formula (CI') is preferable from the viewpoint of sensitivity and alkali developability.

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 means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylene. Examples include tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred; is more preferable.
These polybasic acids may be used alone or in combination of two or more.

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

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

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

In formula (CII), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or a substituent. Represents an optional alkenyl group.

( ^R4 )
In formula (CII), R ⁴ represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent.
Examples of the alkyl group for 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, particularly preferably 8 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and 14 or less. It is even more preferable, and 12 or less is particularly preferable. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 3 to 16 carbon atoms, even more preferably 5 to 14 carbon atoms, and particularly preferably 8 to 12 carbon atoms.

Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. From the viewpoint of developability, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , acryloyl group, and methacryloyl group. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the aromatic ring group for R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably 6 to 22 carbon atoms, even more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 18 carbon atoms.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring. ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. , oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, Examples include benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. .
From the viewpoint of developability, a benzene ring group and a naphthalene ring group are preferable, and a benzene ring group is more preferable.
Examples of substituents that the aromatic ring group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, and epoxy group. , oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the alkenyl group for R ⁴ include linear, branched or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.

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

Examples of substituents that the alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. can be mentioned. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

R ⁴ represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent, and has an effect on developability and film strength. From this point of view, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by formula (CII), (c1) In the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, The content of the partial structure represented by formula (CII) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, Moreover, it is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. When the content is equal to or more than the lower limit, the alkali solubility tends to improve, and when the content is equal to or less than the upper limit, the storage stability of the colored resin composition tends to improve. The above upper and lower limits can be arbitrarily combined. For example, the content of the partial structure represented by formula (CII) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%. , more preferably 10 to 50 mol%, particularly preferably 20 to 40 mol%.

(c1) When the acrylic copolymer resin contains a partial structure represented by formula (CI), the other partial structure included is represented by the following general formula (CIII) from the viewpoint of suppressing brightness reduction by improving heat resistance. Preferably, a partial structure is included.

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

( ^R6 )
In formula (CIII), R ⁶ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxy group, a carboxy group, Represents a halogen atom, an alkoxy group that may have a substituent, a thiol group, or an alkyl sulfide group that may have a substituent.
Examples of the alkyl group for R ⁶ 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, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. is particularly preferred. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 3 to 16 carbon atoms, even more preferably 3 to 14 carbon atoms, and particularly preferably 5 to 12 carbon atoms.

Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. From the viewpoint of heat resistance, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , acryloyl group, and methacryloyl group. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the alkenyl group for R ⁶ include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.

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

Examples of the alkynyl group for R ⁶ include linear, branched or cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the alkynyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.

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

Examples of substituents that the alkynyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. can be mentioned. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

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

Examples of the alkoxy group for R ⁶ include linear, branched, or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 1 to 16 carbon atoms, even more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

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, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , acryloyl group, and methacryloyl group. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the alkyl sulfide group for R ⁶ include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

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

Examples of substituents that the alkyl group in the alkyl sulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, and phenyl group. group, carboxy group, acryloyl group, and methacryloyl group. From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

R ⁶ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group , represents a hydroxyalkyl group, a thiol group, or an alkyl sulfide group that may have a substituent, and from the viewpoint of developability, a hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.

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

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by formula (CIII), (c1) In 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, even more preferably 5 mol% or more, particularly preferably 8 mol% or more, Further, it is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. Setting the value above the lower limit tends to improve heat resistance and suppressing a decrease in brightness, and setting the value below the upper limit increases the content of other partial structures and tends to improve alkali solubility. . The above upper and lower limits can be arbitrarily combined. For example, the content of the partial structure represented by formula (CIII) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 1 to 50 mol%, more preferably 2 to 40 mol%. , 5 to 30 mol% is more preferable, and 8 to 20 mol% is particularly preferable.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the formula (CI), the following general formula (CIV ) is also preferable.

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

(c1) When containing a partial structure represented by formula (CIV) in an acrylic copolymer resin having an ethylenically unsaturated group in its side chain, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in its side chain The content ratio of the partial structure represented by formula (CIV) in is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and 80 mol% or less. It is preferably 70% by mole or less, more preferably 60% by mole or less. When the content is equal to or more than the lower limit, the alkali solubility tends to improve, and when the content is equal to or less than the upper limit, the storage stability of the colored resin composition tends to improve. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the partial structure represented by formula (CIV) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 5 to 80 mol%, and more preferably 10 to 70 mol%, More preferably 20 to 60% mole.

(C) The acid value of the alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 40 mgKOH/g or more, even more preferably 50 mgKOH/g or more, and even more preferably 60 mgKOH/g. The above is particularly preferable, and also preferably 300 mgKOH/g or less, more preferably 250 mgKOH/g or less, even more preferably 200 mgKOH/g or less, and even more preferably 150 mgKOH/g or less. When the content is equal to or more than the lower limit, the alkali solubility tends to improve, and when the content is equal to or less than the upper limit, the storage stability of the colored resin composition tends to improve. The above upper and lower limits can be arbitrarily combined. For example, the acid value of the alkali-soluble resin (C) is preferably 10 to 300 mgKOH/g, more preferably 30 to 300 mgKOH/g, even more preferably 40 to 250 mgKOH/g, even more preferably 50 to 200 mgKOH/g, and even more preferably 60 to 300 mgKOH/g. 150 mgKOH/g is particularly preferred.

The weight average molecular weight of the alkali-soluble resin (C) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 4,000 or more, even more preferably 6,000 or more, particularly preferably 7,000 or more, particularly preferably 8,000. or more, and is preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, particularly preferably 10,000 or less. When the content is equal to or more than the lower limit, heat resistance and coating film curability tend to improve, and when the content is equal to or less than the upper limit, alkali solubility tends to improve. The above upper and lower limits can be arbitrarily combined. For example, the weight average molecular weight of the alkali-soluble resin (C) is preferably from 1,000 to 30,000, more preferably from 2,000 to 30,000, even more preferably from 4,000 to 20,000, even more preferably from 6,000 to 20,000, even more preferably from 7,000 to 15,000, and even more preferably from 8,000 to 15,000. 10,000 is particularly preferred.

The content ratio of the alkali-soluble resin (C) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more in the total solid content of the colored resin composition. % or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and 50% by mass or less. % or less is particularly preferable. Setting the amount at or above the lower limit tends to improve the coating film curability upon exposure to ultraviolet rays, and setting the amount at or below the upper limit tends to improve solubility in the developer and suppress residues. The above upper and lower limits can be arbitrarily combined. For example, the content of the alkali-soluble resin (C) in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 80% by mass, and more preferably 20 to 70% by mass in the total solid content of the colored resin composition. %, even more preferably 30 to 60% by weight, particularly preferably 40 to 50% by weight.

[1-4] (D) Photopolymerization initiator The colored resin composition in the present invention contains (D) a photopolymerization initiator. (D) By containing a photopolymerization initiator, film curability can be imparted by photopolymerization.
(D) The photopolymerization initiator can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an optionally added additive such as a sensitizing dye. The photopolymerization initiation system is a component that has the function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate polymerization-active radicals.

Examples of the photopolymerization initiator include metallocene compounds containing titanocene compounds described in Japanese Patent Application Laid-open Nos. 59-152396 and 61-151197, and Japanese Patent Applications 10-39503. Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters described in publications Examples include radical activators such as, α-aminoalkylphenone compounds, and oxime ester initiators described in Japanese Patent Application Publication No. 2000-80068.

Specific examples of photopolymerization initiators that can be used in the present invention are listed below.
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 Halomethylated triazine derivatives such as -ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine;

2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxa Diazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 , 4-oxadiazole and other halomethylated oxadiazole derivatives;
2-(2'-chlorophenyl)-4,5-diphenylimidasole 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, (4'-methoxyphenyl)-4,5-diphenyl Imidazole derivatives such as imidazole dimers;
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-t-butylanthraquinone, 1-chloroanthraquinone;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p -isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 1,1,1 - Acetophenone derivatives such as trichloromethyl-(p-butylphenyl)ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dicyclopentadienyl -Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl-Ti-2,6-difluoro Phenyl, dicyclopentadienyl-Ti-2,4-difluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dimethylcyclopentadienyl-Ti-bis -2,6-difluorophenyl, dicyclopentadienyl-Ti-2,6-difluoro-3-(pyr-1-yl)-phenyl and other titanocene derivatives;

2-Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone α-Aminoalkylphenone compounds such as;
1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-1-(O-acetyloxime) and other oxime ester compounds.

From the viewpoint of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals, so they are highly sensitive even in small amounts and are stable against thermal reactions. Therefore, it is possible to design a highly sensitive colored resin composition in a small amount. In particular, from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, oxime ester compounds having a carbazole ring which may have a substituent are preferred.

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

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

The number of carbon atoms in the alkyl group in R ^21a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity to exposure, it is preferably 1 or more, more preferably 2 or more, and 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 arbitrarily combined. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, even more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, and a propyl group.
Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group and N-acetyl-N-acetoxyamino group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.

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

Examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and a fluorenyl group. From the viewpoint of developability, a phenyl group, a naphthyl group, and a fluorenyl group are preferable, and a phenyl group and a fluorenyl group are more preferable.
Examples of substituents that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxy group, a halogen atom, Examples include an amino group, an amide group, and an alkyl group. From the viewpoint of developability, a hydroxyl group and a carboxy group are preferred, and a carboxy group is more preferred. Examples of the substituent in the alkyl group which may have a substituent or the alkoxy group which may have a substituent 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 that may have a substituent, more preferably an unsubstituted alkyl group, and even 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 and sensitivity to exposure to light, a carbazolyl group that may have a substituent, a thioxanthonyl group that may have a substituent, a diphenyl sulfide group that may have a substituent, or A fluorenyl group which may have a substituent, and a group in which these groups are connected to a carbonyl group are preferred. From the viewpoint of light absorption to the i-line (365 nm) of the exposure light source, a carbazolyl group that may have a substituent or a group in which a carbazolyl group that may have a substituent and a carbonyl group are preferred.

Examples of substituents that the carbazolyl group may have include alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; F, Halogen atoms such as Cl, Br, I; acyl groups having 1 to 10 carbon atoms; alkyl ester groups having 1 to 10 carbon atoms; alkoxycarbonyl groups having 1 to 10 carbon atoms; halogenated alkyl groups having 1 to 10 carbon atoms; Aromatic ring group having 4 to 10 carbon atoms; Amino group; Aminoalkyl group having 1 to 10 carbon atoms; Hydroxyl group; Nitro group; CN group; Arylyl group which may have a substituent; a heteroaryloyl group which may have a substituent; and a thenoyl group which may have a substituent.

The number of carbon atoms in the alkanoyl group in ^R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, more preferably 3 or more, and preferably 20 or less, more preferably 15 or less, and It is preferably 10 or less, particularly preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, the alkanoyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, even more preferably 2 to 10 carbon atoms, even more preferably 2 to 5 carbon atoms, and particularly preferably 3 to 5 carbon atoms.
Examples of the alkanoyl group include an acetyl group, an ethyl group, a propanoyl group, and a butanoyl group.
Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups, and from the viewpoint of ease of synthesis, unsubstituted It is preferable.

The number of carbon atoms in the aryloyl group in ^R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, more preferably 8 or more, and preferably 20 or less, more preferably 15 or less, and Preferably it is 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the aryloyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, even more preferably 7 to 10 carbon atoms, and particularly preferably 8 to 10 carbon atoms.
Examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of substituents that the aryloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group.From the viewpoint of ease of synthesis, unsubstituted groups are preferable. preferable.

Examples of the compound represented by the formula (I-1) include compounds represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption to the i-line (365 nm) of the exposure light source. It will be done.

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

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

The number of carbon atoms in the alkyl group in ^R24a is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably It is 10 or less, particularly preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, even more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, and cyclohexyl group.
Examples of substituents that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.

The number of carbon atoms in the aryloyl group in ^R24a is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 7 or more, more preferably 8 or more, even more preferably 9 or more, and preferably 20 or less, more preferably It is 15 or less, more preferably 10 or less, particularly preferably 9 or less. The above upper and lower limits can be arbitrarily combined. For example, the aryloyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15 carbon atoms, even more preferably 9 to 10 carbon atoms, and particularly preferably 9 carbon atoms.
Examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a carbonyl group, a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, an ethyl group is preferred.

The number of carbon atoms in the heteroaryloyl group in ^R24a is not particularly limited, but from the viewpoint of solubility in solvents, it is preferably 7 or more, more preferably 8 or more, even more preferably 9 or more, and preferably 20 or less, more It is preferably 15 or less, more preferably 10 or less, particularly preferably 9 or less. The above upper and lower limits can be arbitrarily combined. For example, the heteroaryloyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15 carbon atoms, even more preferably 9 to 10 carbon atoms, and particularly preferably 9 carbon atoms.
Examples of the heteroaryl group include a benzoyl group, a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.
Examples of the substituents that the heteroaryloyl group may have include a carbonyl group, a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group. From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
From the viewpoint of sensitivity, R ^24a is preferably an aryloyl group which may have a substituent, and more preferably a benzoyl group.

The benzene ring constituting the carbazole ring may be further fused with an aromatic ring to form a polycyclic aromatic ring.

Examples of commercially available oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Strong Electronics New Materials, and N-1919 manufactured by ADEKA. , NCI-930, and NCI-831.

Specific examples of oxime ester compounds include the following compounds.

These photopolymerization initiators may be used alone or in combination of two or more.

(D) In addition to the photopolymerization initiator, a chain transfer agent may also be used. A chain transfer agent is a compound that has the function of receiving generated radicals and transferring the received radicals to other compounds.
As the chain transfer agent, various chain transfer agents can be used as long as they are compounds having the above functions, but examples include compounds containing a mercapto group and carbon tetrachloride, which tend to have a high chain transfer effect. Therefore, it is more preferable to use a mercapto group-containing compound. This is thought to be because bond cleavage is likely to occur due to the small S--H bond energy, and hydrogen abstraction reactions and chain transfer reactions are likely to occur. Effective for improving sensitivity and surface hardening.

Examples of mercapto group-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, Mercapto group-containing compounds with aromatic rings such as β-mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, Ethylene glycol bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, penta Erythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol 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-mercaptobutyloxyethyl)-1,3,5 Examples include aliphatic mercapto group-containing compounds such as -triazine-2,4,6(1H,3H,5H)-trione. From the viewpoint of surface smoothness, compounds having multiple mercapto groups are preferred.

As the mercapto group-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable, 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-Mercaptobutyrate), Pentaerythritol Tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, such as trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tris (3-mercaptopropionate). pionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyrate) (oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred, and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) ) is more preferable.
These chain transfer agents may be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (D) is not particularly limited, but is preferably 0.5% by mass or more, and 0.8% by mass or more in the total solid content of the colored resin composition. is more preferably 1.0% by mass or more, further preferably 1.2% by mass or more, further preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and 4% by mass or less. Particularly preferably less than % by mass. Setting the amount above the lower limit value tends to improve the curability of the coating film, and setting it below the upper limit value tends to improve the brightness by reducing visible light absorption. The above upper and lower limits can be arbitrarily combined. For example, in the colored resin composition, the content ratio of the photopolymerization initiator (D) is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass in the total solid content of the colored resin composition. , more preferably 1.0 to 6% by weight, particularly preferably 1.2 to 4% by weight.

When the colored resin composition of the present invention contains a chain transfer agent, its content is not particularly limited, but it is preferably 0.1% by mass or more, and 0.2% by mass or more in the total solid content of the colored resin composition. is more preferable, more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and preferably 3% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less. , 1.5% by mass or less is particularly preferred. When the content is equal to or more than the lower limit, solvent resistance tends to be improved, and when the content is equal to or less than the upper limit, storage stability tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a chain transfer agent, the content thereof is preferably 0.1 to 3% by mass, and 0.2 to 2.5% by mass in the total solid content of the colored resin composition. It is more preferably 0.3 to 2% by mass, even more preferably 0.4 to 1.5% by mass.

[1-5]
The colored resin composition in the present invention contains (E) a photopolymerizable monomer.
(E) The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound"). ) is preferred. The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and hardening due to the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept that includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule as the photopolymerizable monomer (E). The number of ethylenic double bonds that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 4 or more, still more preferably 5 or more, and Preferably it is 8 or less, more preferably 7 or less. Setting the value above the lower limit value tends to result in high sensitivity, and setting the value below the upper limit value tends to improve the solubility in a solvent. The above upper and lower limits can be arbitrarily combined. For example, the number of ethylenic double bonds that the polyfunctional ethylenic monomer has is preferably 2 to 8, more preferably 2 to 7, even more preferably 4 to 7, and particularly preferably 5 to 7.

Examples of ethylenic compounds include unsaturated carboxylic acids, esters of unsaturated carboxylic acids and monohydroxy compounds, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, and aromatic polyhydroxy compounds and unsaturated carboxylic acids. esters obtained by the esterification reaction between unsaturated carboxylic acids and polyhydric carboxylic acids and polyhydric hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polyisocyanate compounds and (meth)acryloyl Examples include ethylenic compounds having a urethane skeleton that are reacted with a containing hydroxy compound.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates can be replaced with methacrylic acid ester, itaconic acid ester, which is replaced with itaconic acid part, crotonic acid ester, which is replaced with crotonic acid part, or maleic acid, which is replaced with maleic acid part. Examples include esters.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid, a polyhydric carboxylic acid, and a polyhydric hydroxy compound is not necessarily a single substance, but may be a mixture. For example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin. can be mentioned.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, isophorone diisocyanate, etc. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3- Examples include reactants with (meth)acryloyl group-containing hydroxy compounds such as hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

Other ethylenic compounds used in the present invention include, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. Preferred are polyfunctional monomers in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol.

One type of these monomers may be used alone, but since it is difficult to use a single compound in production, two or more types may be used in combination. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. Setting the value above the lower limit tends to improve development and dissolution characteristics, and setting the value below the upper limit allows for better manufacturing and handling, resulting in improved photopolymerization performance, pixel surface smoothness, etc. It tends to improve curing properties. Therefore, when using two or more types of polyfunctional monomers with different acid groups, or when using polyfunctional monomers that do not have acid groups together, the acid groups as a whole of the polyfunctional monomers should be adjusted so that they fall within the above range. is preferred.

In the present invention, more preferable polyfunctional monomers having acid groups include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinate ester commercially available as TO1382 manufactured by Toagosei Co., Ltd. as main components. It is a mixture of This polyfunctional monomer and other polyfunctional monomers can also be used in combination. Furthermore, polyfunctional monomers described in paragraphs [0056] and [0057] of Japanese Patent Application Publication No. 2013-140346 can also be used.

In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of the edges of pixels, it is preferable to use the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195971.
From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, it is preferable to use the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195974.

The content of the photopolymerizable monomer (E) in the colored resin composition of the present invention is not particularly limited, but is more than 0% by mass, preferably 5% by mass or more, more preferably 5% by mass or more in the total solid content of the colored resin composition. 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and even more It is preferably 40% by mass or less, particularly preferably 30% by mass or less. When the amount is equal to or more than the lower limit, the curability of the coating film tends to increase, and when it is equal to or less than the upper limit, a decrease in alkali developability tends to be suppressed. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the photopolymerizable monomer (E) in the colored resin composition is preferably more than 0% by mass and 70% by mass or less, more preferably 5 to 60% by mass, and 10% by mass or less, more preferably 5 to 60% by mass, based on the total solid content of the colored resin composition. It is more preferably from 15 to 40% by weight, even more preferably from 15 to 40% by weight, particularly preferably from 20 to 30% by weight.

[1-6] Other solid contents The colored resin composition of the present invention may further contain solid contents other than the above-mentioned components, if necessary. Examples of such components include dispersants, dispersion aids, surfactants, and adhesion improvers.

[1-6-1] Dispersant, dispersion aid When the colored resin composition of the present invention contains a pigment as the colorant (A), it is preferable to contain a dispersant for the purpose of stably dispersing the pigment. Among the dispersants, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time.
Examples of polymeric dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. Examples include system dispersants.
Examples of polymer dispersants include trade names such as EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK Chemie), DISPARON (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Lubricant Chemicals). (manufactured by Sol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the dispersant described in Japanese Patent Application Publication No. 2013-119568.

As the polymer dispersant, from the viewpoint of dispersibility and storage stability, a block copolymer having a functional group containing a nitrogen atom is preferable, and an acrylic block copolymer having a functional group containing a nitrogen atom is more preferable.
The block copolymer having a functional group containing a nitrogen atom consists of an A block having a quaternary ammonium base and/or an amino group in the side chain, and a B block having no quaternary ammonium base and amino group. AB block copolymers and BAB block copolymers are preferred.

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

In formula (d1), R ¹ and R ² each independently have a hydrogen atom, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent. R ¹ and R ² may be bonded to each other to form a cyclic structure. R ³ is a hydrogen atom or a methyl group. X is a divalent linking group.

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

The number of carbon atoms in the optionally substituted aryl group in R ¹ and R ² of formula (d1) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and more preferably 12 or less. It is preferably 8 or less, and more preferably 8 or less. For example, the number is preferably 6 to 16, more preferably 6 to 12, and even more preferably 6 to 8.
Examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, and anthracenyl group. A phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.

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

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

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

In formula (d1), the cyclic structure formed by bonding R ¹ and R ² to each other includes, for example, a 5- to 7-membered nitrogen-containing monocyclic ring or a condensed ring formed by condensing two of these. . The nitrogen-containing heterocycle is preferably non-aromatic, and more preferably a saturated ring. Specifically, the following cyclic structure (IV) can be mentioned, for example.

These cyclic structures may further have a substituent.

In formula (d1), the divalent linking group X is, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ¹³ - group, a -COOR ¹⁴ - group , R ¹³ and R ¹⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, preferably a -COO-R ¹⁴ - group. It is.

The content ratio of the repeating unit represented by formula (d1) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and 15 mol%. % or more, even more preferably 20 mol% or more, particularly preferably 25 mol% or more, and preferably 90 mol% or less, more preferably 70 mol% or less, even more preferably 50 mol% or less, and 40 mol% or less. % or less is particularly preferable. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be arbitrarily combined. For example, the content of the repeating unit represented by formula (d1) in all repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and 10 to 70 mol%. It is more preferably 15 to 70 mol%, even more preferably 20 to 50 mol%, and 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 increasing the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability.

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

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

The content ratio of the repeating unit represented by formula (d2) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and The content is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When it is within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability. The above upper and lower limits can be arbitrarily combined. For example, the content of the repeating unit represented by formula (d2) in all repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol%. More preferred.

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

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

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

The number of carbon atoms in the optionally substituted aryl group in R ⁸ of formula (d3) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and more preferably 12 or less. For example, 6 to 16 is preferable, and 6 to 12 is more preferable.
Examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, and an anthracenyl group. A phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group are preferable, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferable.

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

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 the substituent that the alkyl group in R ⁸ may have include a halogen atom and an alkoxy group.
Examples of substituents 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 straight chain and branched chain alkyl groups.

The content of the repeating unit represented by formula (d3) in all repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and It is preferably 80 mol% or less, more preferably 70 mol% or less. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness. The above upper and lower limits can be arbitrarily combined. For example, the content of the repeating unit represented by formula (d3) in all repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and 50 to 70 mol%. More preferred.

The block copolymer may have repeating units other than the repeating unit represented by formula (d1), the repeating unit represented by formula (d2), and the repeating unit represented by formula (d3). Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Examples include repeating units derived from (meth)acrylamide monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.

From the viewpoint of further improving dispersibility, it is a block copolymer having an A block having a repeating unit represented by formula (d1) and a B block not having a repeating unit represented by formula (d1). It is preferable. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. It is more preferable that the B block has a repeating unit represented by formula (d2) and/or a repeating unit represented by formula (d3).

Repeating units other than the repeating unit represented by formula (d1) may be contained in the A block. Examples of such repeating units include the above-mentioned repeating units derived from (meth)acrylic acid esters. 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 even more preferably 0 mol%.

Repeating units other than the repeating unit represented by formula (d2) and the repeating unit represented by formula (d3) may be contained in the B block. Examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Examples include repeating units derived from (meth)acrylamide monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than the repeating unit represented by formula (d2) and the repeating unit represented by formula (d3) in block B is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. , more preferably 0 mol %.

The acid value of the block copolymer is preferably lower from the viewpoint of dispersibility, particularly preferably 0 mgKOH/g.
Here, the acid value represents the number of mg of KOH required to neutralize 1 g of solid content of the dispersant.

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

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

Block copolymers can be produced by known methods. For example, it can be produced by living polymerization of monomers into which each of the repeating units described above is introduced.
As the living polymerization method, for example, Japanese Patent Application Publication No. 9-62002, Japanese Patent Application Publication 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), Koichi Miguchi, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. The known method described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.

When the colored resin composition of the present invention contains a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.001% by mass or more, and 0.01% by mass in the total solid content of the colored resin composition. The above is more preferable, 0.1% by mass or more is still more preferable, 1% by weight or more is even more preferable, 2% by weight or more is especially preferable, 25% by weight or less is preferable, 20% by weight or less is more preferable, 15 It is more preferably at most 10% by mass, particularly preferably at most 10% by mass. When the content is equal to or more than the lower limit, dispersibility and storage stability tend to improve, and when the content is equal to or less than the upper limit, electrical reliability and developability tend to improve. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a dispersant, the content of the dispersant is preferably 0.001 to 25% by mass, more preferably 0.01 to 25% by mass in the total solid content of the colored resin composition. , more preferably 0.1 to 20% by weight, even more preferably 1 to 15% by weight, particularly preferably 2 to 10% by weight.

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 with respect to 100 parts by mass of the pigment. More preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass. The amount is preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less. By setting it within the above range, there is a tendency that a colored resin composition with excellent dispersion stability and high brightness can be obtained. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a pigment and a dispersant, the content of the dispersant is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, and 10 to 100 parts by mass. It is more preferably from 15 to 40 parts by weight, even more preferably from 15 to 40 parts by weight, and particularly preferably from 20 to 30 parts by weight.

When the colored resin composition of the present invention contains a pigment, it may contain, for example, a pigment derivative as a dispersion aid in order to improve the dispersibility and dispersion stability of the pigment.
Specific examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, and perylene. Examples include derivatives of perinone, diketopyrrolopyrrole, and dioxazine pigments. Substituents for pigment derivatives include, for example, sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, and amide groups directly on the pigment skeleton, or alkyl groups and aryl groups. , a heterocyclic group, etc., preferably a sulfonamide group, a quaternary salt thereof, or a sulfonic acid group, more preferably a sulfonic acid group. Furthermore, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions may be used. 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, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, Examples include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

[1-6-2] Surfactant The colored resin composition in the present invention may contain a surfactant, and examples of the surfactant include anionic, cationic, nonionic, amphoteric surfactants, etc. Although various surfactants can be used, nonionic surfactants are preferred since they are less likely to adversely affect various properties. When the colored resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.001% by mass or more in the total solid content of the colored resin composition. .01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and preferably 10% by mass or less, more preferably 1% by mass or less, even more preferably 0.5% by mass. % or less, particularly preferably 0.3% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and more preferably 0.05 to 0.5% by mass based on the total solid content of the colored resin composition. is more preferred, and 0.1 to 0.3% by mass is particularly preferred.

[1-6-3] Adhesion Improver The colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. Examples of adhesion improvers include silane coupling agents and titanium coupling agents. Silane coupling agents are 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 Silicone Co., Ltd.), and Z-6040. , Z-6043, and Z-6062 (manufactured by Dow Corning Toray Industries). 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 adhesion improver other than the silane coupling agent. Examples include phosphoric acid adhesion improvers and other adhesion improvers.

As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferred. Phosphoric acid-based adhesion improvers represented by the following general formulas (g1), (g2), and (g3) are preferred.

In formulas (g1), (g2), and (g3), R ⁵¹ each independently represents a hydrogen atom or a methyl group. l and l' each independently represent an integer of 1 to 10, and m each independently represents 1, 2 or 3.
Other adhesion improvers include, for example, TEGO (registered trademark) Add Bond LTH (manufactured by Evonik). These phosphoric acid-based adhesion improvers and other adhesives may be used alone or in combination of two or more.

When the colored resin composition in the present invention contains an adhesion improver, its content is not particularly limited, but it is preferably 0.1% by mass or more, and 0.2% by mass or more in the total solid content of the colored resin composition. is more preferably 0.3% by mass or more, further preferably 0.4% by mass or more, further preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less. , 1% by mass or less is particularly preferred. When the content is equal to or more than the lower limit, patterning properties tend to be improved and pattern adhesion under high humidity conditions tends to be improved, and when the content is equal to or less than the upper limit, the generation of residue tends to be suppressed. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains an adhesion improver, the content thereof is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, and 0.3 to 2% by mass based on the total solid content. More preferably 1.5% by weight, particularly preferably 0.4 to 1% by weight.

[2] Preparation of colored resin composition Next, a method for preparing the colored resin composition in the present invention will be explained.

(A) When preparing a colorant containing a pigment, first weigh the pigment, solvent, and dispersant in predetermined amounts, and in a dispersion treatment step, disperse the colorant containing the pigment to prepare a pigment dispersion. . In this dispersion treatment step, for example, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, or homogenizer can be used. By performing this dispersion treatment, the colorant is made into fine particles, so that the coating properties of the colored resin composition are improved, and the transmittance of pixels on the color filter substrate of the product is improved.

When dispersing the pigment, as mentioned above, it is preferable to use a dispersion aid or the like as appropriate.
When performing the dispersion treatment using a sand grinder, it is preferable to use glass beads or zirconia beads with a diameter of 0.1 to several mm. The temperature during the dispersion treatment is preferably set in a range of 0°C or higher, more preferably room temperature or higher, and preferably 100°C or lower, more preferably 80°C or lower. Note that the dispersion time may be adjusted as appropriate, since the appropriate time varies depending on the composition of the pigment dispersion liquid, the size of the sand grinder, and the like.

A solvent, an alkali-soluble resin, a photopolymerization initiator, a photopolymerizable monomer, and components other than the above as necessary are mixed into the pigment dispersion obtained by the dispersion treatment to form a uniform dispersion. In each of the dispersion treatment step and the mixing step, fine dust may be mixed in, so it is preferable to filter the obtained pigment dispersion liquid using a filter or the like.

(A) If the colorant does not contain pigment, mix the colorant, solvent, alkali-soluble resin, photopolymerization initiator, photopolymerizable monomer, and other components as necessary to form a uniform solution. Obtainable. It is preferable to filter the obtained solution using a filter or the like.

[3] Method for manufacturing a color filter Next, a method for manufacturing a color filter of the present invention will be described.
The method for manufacturing a color filter of the present invention includes a pixel forming step of forming pixels on a substrate using a colored resin composition, and the pixel forming step includes a coating step of applying the colored resin composition on the substrate; The method includes a pre-baking step of pre-baking the coating film obtained in the coating step.
The color filter manufacturing method of the present invention may include a black matrix forming step of forming a black matrix on a substrate.

[3-1] Substrate (support)
The substrate to which the colored resin composition is applied is preferably a transparent substrate, and the material is not particularly limited as long as it is transparent and has appropriate strength. Materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly(meth)acrylics. Examples include thermosetting resin sheets such as resin based resins, and various types of glasses. Among these, glass or heat-resistant resin is preferred from the viewpoint of heat resistance.

In order to improve surface properties such as adhesion, the substrate to which the colored resin composition is applied and the substrate provided with the black matrix described below may be treated with corona discharge treatment, ozone treatment, a silane coupling agent, or a urethane-based A thin film formation process using various resins such as resin may also be performed. 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, it is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm. Further, when performing a thin film forming treatment 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, it is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[3-2] Black matrix forming step The color filter manufacturing method of the present invention may include a black matrix forming step of forming a black matrix on the substrate. For example, a color filter can be manufactured by providing a black matrix and then further forming red, green, and blue pixels.

The black matrix is formed on a substrate using a light-shielding metal thin 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, and nickel and tungsten alloys are used, and a plurality of layers of these may be used.
A metal light-shielding film is generally formed by a sputtering method. After forming a desired film pattern using a positive photoresist, for chromium, a mixture of ceric ammonium nitrate and perchloric acid and/or nitric acid is used. Other materials are etched using an etching solution appropriate for the material, and finally the positive photoresist is removed using a special remover to form a black matrix. can.

When using a light-shielding metal thin film, first, a thin film of these metals or metal oxides is formed on a transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of a colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as a stripe, mosaic, or triangle to form a resist image. Thereafter, this coating film can be subjected to an etching process to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form a black matrix. For example, one or more black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. A black matrix can be formed using a colored resin composition containing a mixed black coloring material in a manner similar to the method for forming red, green, and blue pixels described below.

[3-3] Pixel formation process The pixel formation process of forming pixels on the substrate includes a coating process of coating a colored resin composition on the substrate, and a prebaking process of prebaking the coating film obtained in the coating process.
In the pixel formation process, for example, a coating process of coating a colored resin composition of one color among red, green, and blue on a substrate provided with a black matrix, a pre-baking process of drying (pre-baking) the obtained coating film, and a coating process. A photomask is placed on the film, and pixels are formed by thermal curing or photocuring as required, through an exposure step of image exposure through this photomask, and a development step. A color filter can be formed by performing these steps on colored resin compositions of three colors: red, green, and blue.
The colored resin composition in the present invention is preferably used as a composition for forming green or blue pixels (resist pattern) among red, green, and blue pixels. For example, on a resin black matrix forming surface formed on a substrate using a green or blue pixel (resist pattern) forming composition, or on a metal black matrix forming surface formed using a chromium compound or other light-shielding metal material. Pixels are formed thereon by performing coating, drying (pre-baking), image exposure, development, and thermosetting or photocuring.

[3-4] Application Step The colored resin composition can be applied onto the substrate by, for example, a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. Among them, the die coating method significantly reduces the amount of colored resin composition used, has no influence from the mist that adheres when using the spin coating method, and furthermore suppresses the generation of foreign matter. , is preferable from a comprehensive viewpoint.

If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell formation process may become difficult. On the other hand, if the thickness of the coating film is too small, it becomes difficult to increase the pigment concentration and achieve the desired level. Color development may not be possible. The thickness of the coating film after drying is preferably 0.2 μm or more, more preferably 0.5 μm or more, even more preferably 0.8 μm or more, and preferably 20 μm or less, more preferably 10 μm. The thickness is more preferably 5 μm or less. The above upper limit and lower limit can be arbitrarily combined, for example, preferably 0.2 to 20 μm, more preferably 0.5 to 10 μm, even more preferably 0.8 to 5 μm.

[3-5] Prebaking step The coating film obtained in the coating step is preferably dried (prebaking) by a drying method using, for example, a hot plate, an IR oven, or a convection oven. After pre-drying, it is preferable to heat again and pre-bake. Conditions for pre-drying can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. The drying temperature and drying time are selected depending on the type of solvent component, the performance of the dryer used, etc. The drying temperature in preliminary drying is preferably 40°C or higher, more preferably 50°C or higher, and preferably 80°C or lower, more preferably 70°C or lower. The above upper and lower limits can be arbitrarily combined. For example, the temperature is preferably 40 to 80°C, more preferably 50 to 70°C. The drying time in preliminary drying is preferably 15 seconds or more, more preferably 30 seconds or more, and preferably 5 minutes or less, more preferably 3 minutes or less. The above upper and lower limits can be arbitrarily combined. For example, the time is preferably 15 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.

The temperature conditions for pre-baking are preferably higher than the pre-drying temperature. In the present invention, specifically, preferably 95°C or higher, more preferably 100°C or higher, still more preferably 105°C or higher, particularly preferably 110°C or higher, and preferably 200°C or lower, more preferably 160°C. Below, the temperature is more preferably 140°C or lower, even more preferably 130°C or lower, particularly preferably 120°C or lower. Setting the amount above the lower limit tends to increase the dissolution rate, and setting it below the upper limit can prevent the binder resin or photopolymerization initiator from decomposing, inducing thermal polymerization, and causing poor development. Tend. The above upper and lower limits can be arbitrarily combined; for example, the pre-bake temperature is preferably 95 to 200°C, more preferably 95 to 160°C, even more preferably 100 to 140°C, and even more preferably 105 to 130°C. More preferably, the temperature is 110 to 120°C.

The drying time in pre-baking depends on the heating temperature, but is preferably 10 seconds or more, more preferably 15 seconds or more, and preferably 10 minutes or less, more preferably 5 minutes or less. The above upper and lower limits can be arbitrarily combined. For example, the time period is preferably 10 seconds to 10 minutes, and more preferably 15 seconds to 5 minutes.

In the prebaking step, it is preferable to set prebaking conditions so that the spectral change rate (/° C.) of the phthalocyanine compound (1), which will be described later, is small. From the viewpoint of dissolution rate, the spectral change rate (/°C) of the phthalocyanine compound (1) is preferably less than 1.0, more preferably 0.8 or less, and even more preferably 0.6 or less. It is preferably 0.4 or less, particularly preferably 0.4 or less.
The spectral change rate (/°C) of the phthalocyanine compound (1) can be adjusted by, for example, the prebaking temperature and drying time.

[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 by overlaying a negative matrix pattern on the coating film obtained through the pre-baking step and irradiating it with an ultraviolet or visible light source through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the above exposure is not particularly limited. Examples of light sources include lamp 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, argon ion lasers, YAG lasers, etc. Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating light with a specific wavelength.

[3-7] Developing Step In the pixel forming step, it is preferable to include a developing step after the exposure step.
After the coating film using the colored resin composition of the present invention is exposed in the above-mentioned exposure step, it is developed on a substrate by passing through a development step in which development is performed using an aqueous solution containing a surfactant and an alkaline compound. can be manufactured by forming an image on it.
This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Examples of alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus. Inorganic alkaline compounds such as acid potassium, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or di-isopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include organic alkaline compounds. These alkaline compounds may be used alone or in combination of two or more.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

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 in combination with aqueous solutions.
There are no particular limitations on the development conditions, but the development temperature is preferably 10°C or higher, more preferably 15°C or higher, even more preferably 20°C or higher, and preferably 50°C or lower, more preferably 45°C or lower, and The temperature is preferably 40°C or lower. The above upper and lower limits can be arbitrarily combined. For example, the temperature is preferably 10 to 50°C, more preferably 15 to 45°C, and even more preferably 20 to 40°C. The developing method can be any method such as an immersion developing method, a spray developing method, a brush developing method, an ultrasonic developing method, or the like.

[3-7] Thermosetting Process In the pixel forming process, it is also preferable to include a thermosetting process after the development process. The temperature in the heat curing step is preferably 100°C or higher, more preferably 150°C or higher, and preferably 280°C or lower, more preferably 250°C or lower. For example, the temperature is preferably 100 to 280°C, more preferably 150 to 250°C. The time in the heat curing step is preferably 5 minutes or more, and preferably 60 minutes or less. For example, 5 to 60 minutes is preferable.

After the above pixel formation process, the formation of one color patterning pixel is completed. By repeating this process sequentially to pattern black, red, green, and blue, a color filter can be manufactured. Note that the order of patterning the four colors is not limited to the above order.

[3-8] Formation of transparent electrode The color filter of the present invention can be used as a part of components of color displays, liquid crystal display devices, etc. by forming transparent electrodes such as ITO on the image as it is. In order to improve surface smoothness and durability, a top coat layer of polyamide, polyimide, or the like may be provided on the image, if necessary. Further, in some applications such as a planar alignment drive system (IPS mode), a transparent electrode may not be formed.

[4] Image display device (panel)
An image display device according to the present invention includes a color filter manufactured by the method for manufacturing a color filter according to the present invention. A method for manufacturing an image display device according to the present invention includes manufacturing an image display device using a color filter manufactured by a method for manufacturing a color filter according to the present invention.
Hereinafter, a liquid crystal display device and an organic EL display device will be described in detail as image display devices.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device of the present invention will be described. In the liquid crystal display device of the present invention, an alignment film is formed on the color filter manufactured by the color filter manufacturing method of the present invention, and after spacers are scattered on the alignment film, the liquid crystal display device is bonded to a counter substrate to form a liquid crystal cell. The liquid crystal cell is formed, liquid crystal is injected into the formed liquid crystal cell, and wires are connected to the counter electrode to complete the process. The alignment film is preferably a resin film such as polyimide. Gravure printing and/or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After the alignment film is hardened by thermal baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface condition that allows adjustment of the tilt of the liquid crystal.

The spacer has a size that corresponds to the gap with the opposing substrate, and is preferably 2 to 8 μm. It is also possible to form a photo spacer (PS) of a transparent resin film on the color filter substrate by photolithography and use this instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

The bonding gap with the counter substrate varies depending on the use of the liquid crystal display device, but is preferably selected in the range of 2 μm or more and 8 μm or less. After bonding to the counter substrate, parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, the pressure is reduced in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the inside of the chamber. . The degree of vacuum in the liquid crystal cell is preferably 1 x 10 ^-2 Pa or less, more preferably 1 x 10 ^-3 Pa or less, and preferably 1 x 10 ^-7 Pa or more, more preferably 1 x 10 ^-6 Pa. That's all. For example, 1×10 ⁻² to 1×10 ⁻⁷ Pa is preferable, and 1×10 ⁻³ to 1×10 ⁻⁶ Pa is more preferable. Further, it is preferable to heat the liquid crystal cell when the pressure is reduced, and the heating temperature is preferably 30°C or higher, more preferably 50°C or higher, and preferably 100°C or lower, and more preferably 90°C or lower. For example, the temperature is preferably 30 to 100°C, more preferably 50 to 90°C.

The temperature is preferably kept at a reduced pressure for at least 10 minutes and at most 60 minutes, and then immersed in the liquid crystal. A liquid crystal display device (panel) is completed by curing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected and sealing it with a UV curing resin.
The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, etc.
Nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, and the like are known as thermotropic liquid crystals, but 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 FIG. A multicolor organic EL device is manufactured by laminating an organic light emitter 500 via an organic protective layer 30 and an inorganic oxide film 40 on a blue color filter in which pixels 20 are formed using the composition.

The organic light emitter 500 can be laminated by sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter. , a method of bonding an organic light emitter 500 formed on a separate substrate onto the inorganic oxide film 40, and the like. The organic EL element 100 manufactured in this manner is applicable to both passive drive type organic EL display devices and active drive type organic EL display devices.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

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

Note that Et in the formula represents ethyl.

<Dispersant A>
A methacrylic AB block copolymer consisting of an A block having a nitrogen atom-containing functional group and a B block having a solvent-philic group. 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 the following: It has a repeating unit represented by formula (5a). The amine value is 120 mgKOH/g and the acid value is less than 1 mgKOH/g.

The content of repeating units represented by the following formulas (1a), (2a), (3a), (4a), and (5a) in all repeating units is less than 1 mol%, 34.5 mol%, and 6 mol%, respectively. .9 mol%, 13.8 mol%, and 6.9 mol%.

<Alkali-soluble resin A>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing the mixture 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 the mixture was further stirred at 120° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 0.7 parts by mass of trisdimethylaminomethylphenol 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 mixture was reacted at 120°C for 3.5 hours. The weight average molecular weight Mw of the thus obtained alkali-soluble resin A measured by GPC in terms of polystyrene was about 9000, the acid value was 24 mgKOH/g, and the double bond equivalent was 260 g/mol.

<Alkali-soluble resin B>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing the mixture 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 the mixture was further stirred at 120° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, and 0.7 parts by mass of trisdimethylaminomethylphenol 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 mixture was reacted at 120° C. for 3.5 hours. The weight average molecular weight Mw of the thus obtained alkali-soluble resin B measured by GPC in terms of polystyrene was approximately 5,700, the acid value was 89 mgKOH/g, and the double bond equivalent was 430 g/mol.

<Alkali-soluble resin C>
The alkali-soluble resin (B-4) described in Japanese Patent Application Publication No. 2020-046655 was used.

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

Meanwhile, in a monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, t-butylperoxy-2-ethyl 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into the chain transfer agent tank, and the temperature of the reaction tank was charged. After the temperature stabilized at 90° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C, and 60 minutes after the completion of the dropwise addition, the temperature was started to rise to 110°C.

After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were placed in a reaction tank, and the mixture was heated at 110°C. The mixture was allowed to react for 9 hours.
After cooling to room temperature, an alkali-soluble resin D having a polystyrene-equivalent weight average molecular weight Mw of 9000, an acid value of 101 mgKOH/g, and a double bond equivalent of 550 g/mol as measured by GPC was obtained.

<Preparation of green dye dispersion A>
As shown 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 acetate as a solvent (derived from dispersant A). (including solvent), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container, and a dispersion treatment was performed for 6 hours using a paint shaker. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare a green dye dispersion A.

<Preparation of yellow pigment dispersion A>
As shown in Table 1, C. I. 11.4 parts by mass of Pigment Yellow 138, 2.9 parts by mass of dispersant A in terms of solid content, 5.7 parts by mass of alkali-soluble resin D in terms of solid content, and 76.0 parts of propylene glycol monomethyl ether acetate as a solvent. Parts by mass (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, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container, and paint was added. Dispersion treatment was performed for 6 hours using a shaker. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare a yellow pigment dispersion liquid A.

<Green/yellow pigment dispersion A>
A colorant mixture (MG-1) described in Japanese Patent Application Publication No. 2020-046655 was used. The colorant mixture (MG-1) contains a phthalocyanine compound (1).

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

<Photopolymerizable monomer B>
Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (A-9550, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

<Photopolymerizable monomer C>
Polyethoxylated tetramethylolmethane tetraacrylate (NK ester ATM-4E, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)

<Photopolymerizable monomer D>
Aronix M-520, manufactured by Toagosei Co., Ltd.

<Photopolymerization initiator A>
Oxime ester compound having the following chemical structure (methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate)

Note that Me in the formula represents methyl.

<Photopolymerization initiator B>
The oxime-based initiator (D-1) described in Japanese Patent Application Publication No. 2020-046655 was used.

<Photopolymerization initiator C>
The oxime-based initiator (D-2) described in Japanese Patent Application Publication No. 2020-046655 was used.

<Chain transfer agent A>
The compound (F-1) described in Japanese Patent Application Publication No. 2020-046655 was used.

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

<Preparation of colored resin composition>
Colored resin compositions 1 to 3 were prepared by mixing the components listed in Table 2 at the solid content ratios listed. In colored resin compositions 1 and 3, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used as solvents so that the total solid content of the colored resin compositions was 15% by mass. The mixing ratio (mass ratio) of PGMEA/PGME in the colored resin composition obtained was 90/10. In addition, in colored resin composition 2, methoxybutyl acetate (MBA) was used as a solvent so that the total solid content of the colored resin composition was 23.5% by mass, and the colored resin composition obtained was The mixing ratio (mass ratio) of MBA and other solvents in the product was 9/91.

<Evaluation of spectrum change degree>
The obtained colored resin composition was spin-coated onto a 50 mm square, 0.7 mm thick glass substrate (manufactured by AGC, AN100) so that the film thickness after thermosetting (baking) was 2.0 μm. After coating and drying under reduced pressure, it was prebaked on a hot plate at the temperature listed in Table 3 for 90 seconds to produce a colored substrate. Further, after drying under reduced pressure in the same manner, instead of pre-baking, heat curing treatment was performed at 230° C. for 20 minutes in a clean oven to create a colored substrate after baking.

For the obtained colored substrate and colored substrate after firing, the spectral transmission spectrum was measured every 1 nm from wavelength 380 nm to 780 nm using a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and was converted into an absorption spectrum. In the absorption spectrum of the colored substrate, the value of absorbance at wavelength n is defined as A ⁿ , and the similar value of the colored substrate after firing is defined as A ₀ ⁿ . At this time, the degree of spectral change was defined by the following formula as an index of how much the absorption spectrum of the colored substrate differs from that of the colored substrate after firing. Table 3 shows the calculated degree of spectral change. The smaller the degree of spectral change in the following formula, the more the phthalocyanine compound (1) forms aggregates during pre-baking and is closer to the state after firing to completely form aggregates.

<Evaluation of spectrum change rate>
From the description in Table 3, by dividing the amount of change in the degree of spectral change between each pre-bake temperature (80, 90, 95, 100, 105, 110°C) by the amount of change in pre-bake temperature, The rate of spectral change (/°C) was calculated.

<Evaluation of dissolution rate>
The above-mentioned colored substrate was developed using a 0.04% by mass potassium hydroxide aqueous solution at a developer temperature of 23° C., and the time required for complete dissolution was measured, and the results are shown in Table 3 below.

As is clear from Table 3, in colored resin compositions 1 to 3, as the pre-bake temperature increases from 80°C, 90°C, 95°C, and 100°C, the value of the degree of spectral change decreases rapidly, and at 95°C or higher, the value of the degree of spectral change decreases rapidly. The amount of decrease will be smaller. Further, as is clear from Table 4, in colored resin compositions 1 to 3, the spectral change rate of phthalocyanine compound (1) becomes smaller at 95° C. or higher.
This is because the higher the prebaking temperature, the easier it is for phthalocyanine compound (1) to form aggregates, and at temperatures above 95°C, almost all phthalocyanine compound (1) forms aggregates, making it difficult for the spectrum to change any further. Conceivable. Further, the dissolution rate shows a similar tendency, and the dissolution rate increases as the temperature increases from 80°C, 90°C, 95°C, and 100°C, and the decrease in the dissolution time becomes smaller at 95°C or higher. This is because the phthalocyanine compound (1) forms an aggregate, and the alkali-soluble resin (C) contained in the colored resin composition forms a complex around it, and the phthalocyanine compound (1) forms an aggregate. It is thought that the dissolution rate was faster than when it was used alone.
By increasing the dissolution rate of the colored resin composition, the development time can be shortened, which can contribute to improving the production efficiency of color filters and the like.

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims

Pixels are formed on a substrate using a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer. A method for manufacturing a color filter, comprising a pixel forming step of forming a pixel,
The pixel forming step includes a coating step of coating the colored resin composition on the substrate, and a pre-baking step of pre-baking the coating film obtained in the coating step,
As the colorant (A), a phthalocyanine compound having a chemical structure represented by the following general formula (1) is used,
The alkali-soluble resin (C) is a resin having a hydroxyl group or a carboxyl group,
A method for manufacturing a color filter, characterized in that the pre-baking temperature is 95°C or higher.

(In formula (1), A 1 to A 16 each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 to A 16 represents a fluorine atom.
In addition, one or more of A 1 to A 4 is a group represented by the following general formula (2), and one or more of A 5 to A 8 is a group represented by the following general formula (2). and one or more of A 9 to A 12 is a group represented by the following general formula (2), and one or more of A 13 to A 16 is a group represented by the following general formula (2). be. )

(In formula (2), X represents a divalent linking group. The benzene ring in formula (2) has a carbonyl group. * represents a bond.)
The method for manufacturing a color filter according to claim 1, wherein the pre-baking temperature is 100°C or higher.
The method for manufacturing a color filter according to claim 1 or 2, wherein the pre-baking temperature is 105°C or higher.
The method for producing a color filter according to any one of claims 1 to 3, wherein the pre-baking temperature is 110°C or higher.
Pixels are formed on a substrate using a colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer. A method for manufacturing a color filter, comprising a pixel forming step of forming a pixel,
The pixel forming step includes a coating step of coating the colored resin composition on the substrate, and a pre-baking step of pre-baking the coating film obtained in the coating step,
As the colorant (A), a phthalocyanine compound having a chemical structure represented by the following general formula (1) is used,
The alkali-soluble resin (C) is a resin having a hydroxyl group or a carboxyl group,
A method for manufacturing a color filter, characterized in that in the prebaking step, the phthalocyanine compound is prebaked so that the spectral change rate is less than 1.0.

(In formula (1), A 1 to A 16 each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A 1 to A 16 represents a fluorine atom.
In addition, one or more of A 1 to A 4 is a group represented by the following general formula (2), and one or more of A 5 to A 8 is a group represented by the following general formula (2). and one or more of A 9 to A 12 is a group represented by the following general formula (2), and one or more of A 13 to A 16 is a group represented by the following general formula (2). be. )

(In formula (2), X represents a divalent linking group. The benzene ring in formula (2) has a carbonyl group. * represents a bond.)
A method for manufacturing an image display device, comprising manufacturing an image display device using a color filter manufactured by the manufacturing method according to any one of claims 1 to 5.