WO2023063336A1

WO2023063336A1 - Colored resin composition, color filter, and image display device

Info

Publication number: WO2023063336A1
Application number: PCT/JP2022/037974
Authority: WO
Inventors: 宏明石井; 紫陽平岡; 幸治福岡; 直也大村
Original assignee: 三菱ケミカル株式会社
Priority date: 2021-10-12
Filing date: 2022-10-12
Publication date: 2023-04-20
Also published as: TW202334326A

Abstract

Provided is a colored resin composition that makes it possible to obtain a cured film having excellent luminance and favorable contrast. This colored resin composition contains a colorant (A), a solvent (B), an alkali-soluble resin (C), a photopolymerization initiator (D), and a photopolymerizable monomer (E). The colorant (A) contains a specific phthalocyanine compound. The alkali-soluble resin (C) contains an alkali-soluble resin (c-1) having repeating units that include an aromatic ring on a side chain. The total content ratio of the repeating units that include the aromatic ring on the side chain in the alkali-soluble resin (c-1) is 20 mol% or higher.

Description

Colored resin composition, color filter and image display device

The present invention relates to a colored resin composition, a color filter and an image display device.
This application claims priority based on Japanese Patent Application No. 2021-167165 filed in Japan on October 12, 2021, 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 them, the pigment dispersion method, which has excellent characteristics on average, is most widely used from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like.

In recent years, there has been a demand for higher brightness, higher contrast, and a wider color gamut for color filters. Pigments are generally used as colorants to determine the color of color filters from the viewpoint of heat resistance and light resistance. The use of dyes instead of pigments as agents has been extensively studied. As for green pixels, the use of a specific phthalocyanine compound as a dye is under investigation (see, for example, Patent Documents 1 to 3).

Japanese Patent Application Laid-Open No. 2019-113732 WO2020/171060 Japanese Patent Application Laid-Open No. 2020-046655

As a result of investigation by the present inventors, it was found that the colored resin compositions described in Patent Documents 1 to 3 do not have sufficient contrast for practical use.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a colored resin composition from which a cured film having good contrast can be obtained.

As a result of intensive studies by the present inventors, it was found that the above problems can be solved by using a specific phthalocyanine compound as a coloring agent and also using an alkali-soluble resin having a specific structure. reached.
That is, the present invention has the following configurations.

[1] A colored resin composition containing (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer,
The (A) colorant contains a phthalocyanine compound having a chemical structure represented by the following general formula (1),
The (C) alkali-soluble resin contains an alkali-soluble resin (c-1) having a repeating unit containing an aromatic ring on a side chain,
When the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100 mol%, the total content of repeating units containing an aromatic ring on the side chain is 20 mol% or more. A colored resin composition.

(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), provided that one or more of A ¹ to A ¹⁶ represents a fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).)

(In Formula (2), X represents a divalent linking group. The benzene ring in Formula (2) may have any substituent. * represents a bond.)
[2] The colored resin composition of [1], wherein in the alkali-soluble resin (c-1), the total content of repeating units containing aromatic rings on the side chains is 30 mol% or more.
[3] [1] or [2], wherein the alkali-soluble resin (c-1) has a repeating unit containing an alicyclic structure on a side chain, and the alicyclic structure is a saturated alicyclic structure; colored resin composition.
[4] The colored resin composition of [3], wherein in the repeating unit containing an alicyclic structure on the side chain, the distance from the main chain to the alicyclic structure is 4 atoms or less.
[5] When the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100 mol%, the total content of repeating units containing an alicyclic structure on the side chain is 10 mol% or less. The colored resin composition of [3] or [4].
[6] As the repeating unit containing an aromatic ring on the side chain of the alkali-soluble resin (c-1), at least one selected from repeating units represented by the following general formulas (3) and (4) The colored resin composition according to any one of [1] to [5], which has seeds.

(In formulas (3) and (4), R ¹ each independently represents a hydrogen atom or a methyl group. The benzene ring in formulas (3) and (4) has an optional substituent. may be used.)
[7] The colored resin composition of [6], wherein the alkali-soluble resin (c-1) has a repeating unit represented by the general formula (3) as a repeating unit containing an aromatic ring on the side chain.
[8] The repeating unit containing an alicyclic structure on the side chain of the alkali-soluble resin (c-1) is selected from repeating units represented by the following general formulas (5) and (6). The colored resin composition according to any one of [3] to [5], which has at least one.

(In formulas (5) and (6), R ¹ each independently represents a hydrogen atom or a methyl group. The saturated hydrocarbon rings in formulas (5) and (6) have optional substituents. may be.)
[9] The colored resin composition of [8], wherein the alkali-soluble resin (c-1) has a repeating unit represented by the general formula (5) as a repeating unit containing an alicyclic structure on the side chain. thing.
[10] The colored resin composition according to any one of [1] to [9], wherein the alkali-soluble resin (c-1) has a repeating unit represented by the following general formula (I).

(In Formula (I), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group.
R ² represents a trivalent hydrocarbon group which may have a substituent.
R ⁴ represents a divalent hydrocarbon group which may have a substituent. )
[11] The colored resin composition according to any one of [1] to [10], wherein the content of (A) the colorant is 10% by mass or more relative to the total solid content of the colored resin composition.
[12] The colored resin composition according to any one of [1] to [11], wherein the content of the alkali-soluble resin (c-1) is 10% by mass or more relative to the total solid content of the colored resin composition. .
[13] A color filter comprising pixels produced using the colored resin composition of any one of [1] to [12].
[14] An image display device comprising the color filter of [13].

According to the present invention, it is possible to provide a colored resin composition that gives a cured film with excellent brightness and good contrast.

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

In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the "amine value" represents the amine value in terms of effective solid content unless otherwise specified, and is a value represented by the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant.
In the present invention, the acid value means an acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.
In the present invention, "C.I." means Color Index.
In the present invention, "total solid content" means all components other than the solvent contained in the colored resin composition. Even if a component other than the solvent is liquid at normal temperature, the component is not included in the solvent but is included in the total solid content.
In the present invention, "(meth)acryl" means "one or both of acryl and methacryl".
Furthermore, in the present invention, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.

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

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

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). At least one of A ¹ to A ¹⁶ represents a fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

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

( ^A1 to ^A16 )
In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by general formula (2) below. At least one of A ¹ to A ¹⁶ represents a fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

Halogen atoms in A ¹ to A ¹⁶ include, for example, fluorine, chlorine and bromine atoms. A fluorine atom is preferable from the viewpoint of adjusting the hue to an optimum hue as a green dye used in a color filter and from the viewpoint of increasing the luminance.

One or more of A ¹ to A ¹⁶ represents a fluorine atom, preferably 6 or more, more preferably 7 or more, still more preferably 8 or more, preferably 15 or less, more preferably 12 or less, and 10 More preferred are: The stability of the phthalocyanine compound (1) tends to be improved by setting it to the lower limit or more, and the affinity with the dispersant or solvent in the colored resin composition is improved by setting it to the upper limit or less. Tend. The above upper and lower limits can be combined arbitrarily. 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 10.

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

(Substituent that the benzene ring may have)
The benzene ring in formula (2) may have any substituent. Although the substituent is not particularly limited, for example, a halogen atom, an alkyl group ( ^-RA group), an alkoxy group ( ^-OR group (where ^RA represents an alkyl group)), an alkoxycarbonyl group (-COOR ^A group (where ^RA represents an alkyl group)), aryl group (-R ^B group), aryloxy group (-OR ^B group (where ^RB represents an aryl group)), aryloxycarbonyl group (-COOR ^B group (R ^B represents an aryl group)). An alkoxycarbonyl group is preferable from the viewpoint of affinity with solvents and brightness.

The alkyl group contained in these groups may be linear, branched, or cyclic, but is preferably linear from the viewpoint of affinity with solvents.
Although the number of carbon atoms in the alkyl group is not particularly limited, it 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. By making it more than the said lower limit, there exists a tendency which suppresses agglomeration and becomes a foreign material suppression. By making it below the said upper limit, there exists a tendency for solvent affinity to improve and aging stability to improve. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-6, more preferably 1-5, and even more preferably 2-4.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, and hexyl group. From the viewpoint of suppressing aggregation, methyl group and ethyl group are preferable, and ethyl group is more preferable.

The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
Although the number of carbon atoms in the aryl group is not particularly limited, it is preferably 4 or more, more preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When the content is at least the above lower limit, aggregation due to steric repulsion tends to be suppressed. When the content is equal to or less than the upper limit, there is a tendency that solvent affinity is improved and stability over time is improved. The above upper and lower limits can be combined arbitrarily. For example, the aryl group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be monocyclic or condensed. Examples of aromatic hydrocarbon ring groups include benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring and heptalene ring having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be monocyclic or condensed. Examples of aromatic heterocyclic groups include furan ring, thiophene ring, pyrrole ring, 2H-pyran ring, 4H-thiopyran ring, pyridine ring, 1,3-oxazole ring and isoxazole ring 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 imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring and pteridine ring.

When the benzene ring in formula (2) has an optional substituent, the number of substituents is not particularly limited. ) and from the viewpoint that the molecules of the phthalocyanine compound (1) associate with each other to improve the contrast, the number of substitutions is preferably one per benzene ring.
When the benzene ring in formula (2) has an optional substituent, the substitution position may be o-position, m-position, or p-position, but π-π between phthalocyanine compound (1) molecules The p- position is preferred. In particular, from the viewpoint of improving contrast, an alkoxycarbonyl group is preferable as the substituent at the p-position.

In formula (1), at least one of A ¹ to A ¹⁶ represents a group represented by formula (2). From the viewpoint of solubility in a solvent and enhancement of brightness and contrast due to π-π stacking between phthalocyanine compound (1) molecules and association of molecules, one or more of A ¹ to A ⁴ has the formula (2 ), at least one of A ⁵ to A ⁸ is a group represented by formula (2), and at least one of A ⁹ to A ¹² is a group represented by formula (2) and one or more of A ¹³ to A ¹⁶ are preferably groups represented by formula (2); two or more of A ¹ to A ⁴ are preferably represented by formula (2) two or more of A ⁵ to A ⁸ are groups represented by formula (2), and two or more of A ⁹ to A ¹² are groups represented by formula (2) and two or more of A ¹³ to A ¹⁶ are groups represented by formula (2).

In formula (1), at least one of A ¹ to A ¹⁶ represents a fluorine atom, but from the viewpoint of the stability of the phthalocyanine compound, at least one of A ¹ to A ⁴ represents a fluorine atom, and A ⁵ It is preferred that at least one of to A ⁸ is a fluorine atom, at least one of A ⁹ to A ¹² is a fluorine atom, and at least one of A ¹³ to A ¹⁶ is a fluorine atom. two or more of A ¹ to A ⁴ are fluorine atoms, two or more of A ⁵ to A ⁸ are fluorine atoms, two or more of A ⁹ to A ¹² are fluorine atoms, and , A ¹³ to A ¹⁶ are more preferably fluorine atoms.

From the viewpoint of the maximum transmission wavelength and transmittance in the phthalocyanine compound (1), affinity with dispersants and solvents in the colored resin composition, uniformity of crystallization of the phthalocyanine compound during firing of the color filter, brightness and contrast, A ² , ^A3 , ^A6 , ^A7 , ^A10 , ^A11 , ^A14 , and ^A15 are groups represented by formula (2), and ^A1 , ^A4 , ^A5 , ^A8 , It is particularly preferred that A ⁹ , A ¹² , A ¹³ and A ¹⁶ are fluorine atoms.

Specific examples of the phthalocyanine compound (1) include the following compounds.

In the above formula, Et represents ethyl.

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.

(A) The coloring agent may contain other coloring agents in addition to the phthalocyanine compound (1). Other colorants include pigments and dyes. When used for green pixels, it is preferable to use, for example, green pigments, green dyes, yellow pigments, and yellow dyes.
Examples of green pigments include C.I. I. Pigment Green 7, 36, 58, 59, 62 and 63, and C.I. I. Pigment Green 58 is preferred.
Among green dyes classified as dyes in the Color Index, C.I. I. Examples of solvent dyes include C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 can be mentioned. 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. I.

Modant Green

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

As a yellow pigment, for example, 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 1:1 complexes of azobarbituric acid with nickel represented by the following formula (i) or tautomers thereof, other compounds is inserted (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

Other compounds inserted in 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 wide color gamut, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 154, 155, 180, 185, nickel azo complexes represented by formula (i) are preferred, and C.I. I. Pigment Yellow 83, 138, 139, 180, 185 and nickel azo complexes represented by formula (i) are more preferred.

Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include specific compounds described in Japanese Patent Application Laid-Open No. 2010-168531.
Among yellow dyes classified as dyes in the Color Index, C.I. I. Examples of solvent dyes include C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 and the like. 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. 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 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, 141. C. I. Examples of modant dyes include C.I. I.

Modant Yellow

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

The average primary particle size of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.04 μm or less. Solvent salt milling, for example, is preferably used for atomization of the pigment.

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

The content of the phthalocyanine compound (1) in the colored resin composition of 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. 10% by mass or more is more preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is even more preferable, and 20% by mass The following are particularly preferred. When the lower limit value or more is used, the luminance tends to be improved, and when the upper limit value or less is used, the stability over time tends to be ensured. The above upper and lower limits can be combined arbitrarily. The above upper and lower limits can be combined arbitrarily. For example, the content of the phthalocyanine compound (1) in the colored resin composition is preferably 3 to 50% by mass, more preferably 5 to 50% by mass, more preferably 10 to 40% by mass in the total solid content of the colored resin composition. More preferably, 15 to 30% by mass is particularly preferable.

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

[1-2] (B) solvent (B) solvent dissolves or disperses the colorant, alkali-soluble resin, photopolymerization initiator, photopolymerizable monomer, and other components in the colored resin composition of the present invention, It has the function of adjusting the viscosity.
(B) Any solvent can be used as long as it can dissolve or disperse each component.

Examples of such solvents 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;
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, methylhexyl ketone, methyl nonyl ketone, methoxymethyl 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, 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-methoxypropionic acid Chain 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, amyl chloride;
ether ketones such as methoxymethylpentanone;
Examples include nitriles such as acetonitrile and benzonitrile.

Commercially available solvents corresponding to the above include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names). These solvents may be used individually by 1 type, and may use 2 or more types together.

When forming pixels of a color filter by photolithography, a solvent having a boiling point in the range of 100 to 200° C. (under pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) is selected. is preferred. A solvent having a boiling point of 120 to 170° C. is more preferred.
Glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, etc. in the solvent and relatively high solubility of the constituent components in the composition.

The glycol alkyl ether acetates may be used alone, or may be used in combination with other solvents. Glycol monoalkyl ethers are particularly preferred as solvents to be used in combination. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of the components in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the colored resin composition to be obtained later tends to decrease, resulting in a decrease in storage stability. When glycol alkyl ether acetates are used in combination, the content of glycol monoalkyl ethers in the solvent (B) is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

As another aspect, a solvent having a boiling point of 150° C. or higher can be used together. By using a solvent having a boiling point of 150° C. or more, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult to destroy the interrelationships of the constituent components in the pigment dispersion due to rapid drying. . When a solvent having a boiling point of 150° C. or higher is used in combination, the content of the solvent having a boiling point of 150° C. or higher in the solvent (B) is preferably 3% to 50% by mass, and 5% to 40% by mass. is more preferred, and 5% by mass to 30% by mass is particularly preferred. By making it equal to or higher than the above lower limit, for example, it tends to be easy to avoid causing foreign matter defects due to precipitation and solidification of coloring material components at the tip of the slit nozzle. It tends to be easy to avoid causing problems such as poor tact time in the vacuum drying process and pre-baking pin marks due to slow drying speed.
The solvent with a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, it is not necessary to separately contain a solvent with a boiling point of 150°C or higher.
Solvents having a boiling point of 150° C. or higher are preferably, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate. , triacetin.

When forming pixels of a color filter by an inkjet method, a solvent having a boiling point of generally 130° C. or higher and 300° C. or lower, preferably 150° C. or higher and 280° C. or lower is suitable. When the content is at least the above lower limit, the uniformity of the resulting coating film tends to be improved, and when the content is at most the above upper limit, the amount of residual solvent during firing tends to be reduced.
From the viewpoint of the uniformity of the coating film to be obtained, the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less.

In the production of color filters using the inkjet method, the ink emitted from the nozzle is very fine, ranging from several pL to several tens of pL. tends to stick. In order to avoid this, the solvent (B) preferably contains a solvent with a high boiling point, specifically a solvent with a boiling point of 180° C. or higher. It is more preferable to contain a solvent with a boiling point of 200° C. or higher, and it is particularly preferable to contain a solvent with a boiling point of 220° C. or higher. When a solvent having a boiling point of 180° C. or higher is used together, the content of the solvent having a boiling point of 180° C. or higher in the solvent (B) is preferably 50% by mass or more, preferably 70% by mass. More preferably, 90% by mass or more is most preferable. By making it more than the said lower limit, there exists a tendency for the evaporation prevention effect of the solvent from a droplet to be fully exhibited easily.

Examples of solvents having a boiling point of 180° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6- Hexanol diacetate, 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 them, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferred.

On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. When alcohols are used together, the alcohol content 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 of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less. When the content is equal to or less than the above upper limit, there is a tendency that the coating film is easily formed. 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 78% by mass or more, in consideration of viscosity suitable for coating. The above upper and lower limits can be combined arbitrarily. For example, the solvent content in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and even more preferably 78 to 85% by mass.

[1-3] (C) Alkali-Soluble Resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility by a developer.
(C) alkali-soluble resin in the colored resin composition of the present invention contains an alkali-soluble resin (c-1) having a repeating unit containing an aromatic ring on a side chain, the alkali-soluble resin (c-1) When the total number of moles of repeating units of is 100 mol %, the total content of repeating units containing aromatic rings on side chains is 20 mol % or more.
Further, the alkali-soluble resin (c-1) preferably has a repeating unit containing an alicyclic structure on its side chain and the alicyclic structure is a saturated alicyclic structure.

By containing the alkali-soluble resin (c-1), the aromatic ring contained in the alkali-soluble resin (c-1) and the phthalocyanine compound (1) approach each other due to π-π stacking of the phthalocyanine compound (1). As shown in Document 2, a specific phthalocyanine compound promotes the association of molecules in the baking process and regular arrangement (crystallization), which is thought to improve the contrast. In addition, when the amount of the alicyclic structure contained is small, it is thought that the bulky alicyclic structure prevents the inhibition of the association between the molecules of the phthalocyanine compound, thereby improving the contrast.

When the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100 mol%, the total content of repeating units containing an aromatic ring on the side chain is 20 mol% or more from the viewpoint of contrast. 30 mol % or more is preferable, and 40 mol % or more is more preferable. From the viewpoint of development patterning properties, it is preferably 70 mol % or less, more preferably 60 mol % or less.

When the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100 mol%, the total content of repeating units containing an alicyclic structure on the side chain is 10 mol% or less from the viewpoint of contrast. is preferred, 5 mol % or less is more preferred, and 2 mol % or less is even more preferred. Although the lower limit is not particularly limited, it is preferably 0.5 mol % or more from the viewpoint of adhesion improvement and undercut suppression.

The repeating unit containing an aromatic ring on the side chain is a repeating unit derived from a monomer containing an aromatic ring on the side chain, among the repeating units formed in the copolymerization reaction for synthesizing the alkali-soluble resin, and the side chain It contains a unit in which an aromatic ring is subsequently introduced onto the side chain by an addition reaction with a compound containing an aromatic ring or an aromatic ring-forming reaction after a copolymerization reaction with respect to a monomer not containing an aromatic ring on the upper side. From the viewpoint of contrast, the repeating unit containing an aromatic ring on its side chain is preferably a repeating unit derived from a monomer containing an aromatic ring on its side chain.
An aromatic ring may be further introduced into the repeating unit derived from a monomer containing an aromatic ring on its side chain by an addition reaction or an aromatic ring-forming reaction with a compound containing an aromatic ring.

Examples of aromatic rings in repeating units containing aromatic rings on side chains include aromatic hydrocarbon rings and aromatic heterocycles. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, and still more preferably 12 or less. For example, 2 to 12 are preferred, and 6 to 12 are more preferred. The heat resistance tends to be improved by adjusting the content to be equal to or higher than the above lower limit. When the content is equal to or less than the upper limit, there is a tendency that solvent affinity is improved and stability over time is improved.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be monocyclic or condensed. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have one free valence, An acenaphthene ring, a fluoranthene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be monocyclic or condensed. Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring and carbazole ring having one free valence. ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, 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 brightness, a benzene ring or naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

These aromatic rings may have a substituent, and the substituent is not particularly limited. Examples include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkenyl group having 2 to 8 carbon atoms; hydroxyl group; alkoxyl group having 1 to 8 carbon atoms: phenyl group, mesityl group, tolyl group, aromatic hydrocarbon ring group such as naphthyl group; cyano group; carboxyl group; Group; C2-9 alkylcarbonyloxy group; sulfonic acid group; sulfamoyl group; C2-9 alkylsulfamoyl group; carbonyl group; C2-9 alkylcarbonyl group; hydroxyethyl group; amide group; dialkylaminoethyl group formed by bonding alkyl group having 1 to 4 carbon atoms; trifluoromethyl group; trialkylsilyl group having 1 to 8 carbon atoms, nitro group, alkylthio group having 1 to 8 carbon atoms. From the viewpoint of ease of synthesis, it is desirable that the alkyl group has 1 carbon atom or does not contain a substituent.

From the viewpoint of ease of synthesis and ease of π-π stacking with the phthalocyanine compound (1), the structure of the repeating unit containing an aromatic ring on the side chain is the following general formula (3), the following general formula It is preferably one or two selected from (4), and more preferably the following general formula (3).

In formulas (3) and (4), each R ¹ independently represents a hydrogen atom or a methyl group. The benzene rings in formulas (3) and (4) may have any substituents.

The repeating unit containing an alicyclic structure on the side chain is a repeating unit derived from a monomer containing an alicyclic structure on the side chain, among the repeating units formed in the copolymerization reaction for synthesizing the alkali-soluble resin. And, for a monomer that does not contain an alicyclic structure on the side chain, after the copolymerization reaction, an alicyclic structure is added to the side chain by an addition reaction with a compound containing an alicyclic structure or a hydrocarbon ring formation reaction. Including introduced units. From the viewpoint of contrast, the repeating unit containing an alicyclic structure on the side chain is a repeating unit derived from a monomer containing an alicyclic structure on the side chain, and in the alkali-soluble resin (c-1) is 100 mol %, the total content of repeating units derived from the monomer containing an alicyclic structure on the side chain is preferably 10 mol % or less.
An alicyclic structure may be further introduced into the repeating unit derived from a monomer containing an alicyclic structure on its side chain by an addition reaction with a compound containing an alicyclic structure or a hydrocarbon ring-forming reaction. do not have.

From the viewpoint of contrast, in the repeating unit containing the alicyclic structure on the side chain, the distance from the main chain to the alicyclic structure is preferably 4 atoms or less, more preferably 2 atoms or less. The total content of repeating units having a distance from the main chain to the alicyclic structure in the above range is within the above content, thereby suppressing inhibition of association between molecules of the phthalocyanine compound (1), It is considered that the contrast is improved.
Here, the fact that the distance from the main chain to the alicyclic structure is 4 atoms or less is included in the binding chain from the joint between the main chain and the side chain of the alkali-soluble resin (c-1) to the alicyclic structure. The number of atoms does not include the carbon atoms that form the bond between the main chain and the side chain and the carbon atoms that constitute the alicyclic structure. For example, the following general formulas (5) and (6) are both counted as having two atoms.

The alicyclic structure in the repeating unit containing the alicyclic structure on the side chain may be a monocyclic ring or a condensed ring. Alicyclic structures include, for example, cyclopropyl ring, cyclobutyl ring, cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctyl ring, norbornane ring, tricyclodecane ring, and adamantane ring. A cyclohexyl ring or a tricyclodecane ring is desirable from the viewpoint of heat resistance and ease of synthesis.
These alicyclic structures are preferably saturated alicyclic structures.

These alicyclic structures may have a substituent, and the substituent is not particularly limited, but examples include halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; Alkyl group; alkenyl group having 2 to 8 carbon atoms; hydroxyl group; alkoxyl group having 1 to 8 carbon atoms: phenyl group, mesityl group, tolyl group, aromatic hydrocarbon ring group such as naphthyl group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfonic acid group; sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; carbonyl group; alkylcarbonyl group having 2 to 9 carbon atoms; an acetylamide group; a dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms; a trifluoromethyl group; a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms; and, from the viewpoint of ease of synthesis, it is desirable that it does not contain a methyl group or a substituent.

The structure of the repeating unit containing an alicyclic structure on the side chain is one or two selected from the following general formulas (5) and (6) from the viewpoint of ease of synthesis and heat resistance. and more preferably the following general formula (5).

In formulas (5) and (6), each R ¹ independently represents a hydrogen atom or a methyl group. The saturated hydrocarbon rings in formulas (5) and (6) may have any substituents.

The alkali-soluble resin (c-1) may further contain other repeating units in addition to repeating units containing an aromatic ring on the side chain and repeating units containing an alicyclic structure on the side chain, and may have the following general formula: It is desirable to have a repeating unit represented by (I).

In formula (I), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group.
R ² represents a trivalent hydrocarbon group which may have a substituent.
R ⁴ represents a divalent hydrocarbon group which may have a substituent.

The carboxy groups in the repeating unit represented by formula (I) are sufficiently separated from the main chain and have high flexibility so that they are exposed to the outside of the resin molecule without forming strong hydrogen bonds between the carboxy groups. easy to be placed in When the alkali-soluble resin (c-1) has a repeating unit represented by the formula (I), the central metal site or ether bond site in the phthalocyanine compound (1) and the carboxy group of the alkali-soluble resin (c-1) By forming a bond such as a hydrogen bond and covering the phthalocyanine compound (1) with the resin, the decomposition reaction of the phthalocyanine compound (1) during firing is inhibited, resulting in high brightness.

( ^R2 )
In formula (I), R ² represents a trivalent hydrocarbon group which may have a substituent. Trivalent hydrocarbons include, for example, trivalent aliphatic hydrocarbon groups. The trivalent aliphatic hydrocarbon group includes a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aliphatic hydrocarbon group combining them. .
The number of carbon atoms in the trivalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, preferably 15 or less, more preferably 10 or less, and 8 or less. More preferably, 5 or less is particularly preferable. Within the above range, hydrogen bonding with the phthalocyanine compound (1) is likely to be formed, and brightness tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, 1 to 15 are preferred, 1 to 10 are more preferred, 2 to 8 are even more preferred, and 3 to 5 are particularly preferred.

Specific examples of trivalent aliphatic hydrocarbon groups include the following. In addition, when it contains an alicyclic structure as in the following general formula (R-2), it is not included in the repeating unit containing an alicyclic structure.

* represents a bond in formulas (R-1) and (R-2).

Examples of substituents that the trivalent hydrocarbon group may have include an alkoxy group, an aryloxy group, an aryloxythio group, and a halogen atom. When the substituent contains an aromatic ring, it is not included in the repeating unit containing the aromatic ring, and when the substituent contains an alicyclic structure, it is not included in the repeating unit containing the alicyclic structure.

( ^R4 )
In formula (I), ^R4 represents a divalent hydrocarbon group which may have a substituent. Divalent hydrocarbons include, for example, divalent aliphatic hydrocarbon groups and divalent aromatic hydrocarbon ring groups.

Examples of the divalent aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aliphatic hydrocarbon group combining them. be done.
The number of carbon atoms in the divalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, particularly preferably 4 or more, and preferably 15 or less, and 10 or less. It is more preferable, 8 or less is more preferable, and 6 or less is particularly preferable. When the value is at least the above lower limit, the hydrogen bond between the phthalocyanine compound (1) and the carboxy group of the alkali-soluble resin (c-1) tends to be formed strongly. The formation of hydrogen bonds between the compound (1) and the carboxy group of the alkali-soluble resin (c-1) tends to be maintained. The above upper and lower limits can be combined arbitrarily. For example, 1 to 15 are preferred, 2 to 10 are more preferred, 3 to 8 are even more preferred, and 4 to 6 are particularly preferred.

Specific examples of divalent aliphatic hydrocarbon groups include ethylene group, propylene group, ethenylene group, cyclohex-4-ene-1,2-diyl group and cyclohexa-1,2-diyl group. Among these, an ethylene group, an ethenylene group, and a cyclohex-4-ene-1,2-diyl group are preferable from the viewpoint of promoting hydrogen bond formation with the carboxy group of the alkali-soluble resin (c-1).

The number of carbon atoms in the divalent aromatic hydrocarbon ring group is not particularly limited, but is preferably 6 or more and preferably 12 or less. For example, 6-12 is preferred. When it is equal to or higher than the lower limit, there is a tendency to promote π-π interaction with the phthalocyanine compound (1), and when it is equal to or lower than the upper limit, the alkali-soluble resin (c-1) is used in the process of producing a color filter. There is a tendency that the reduction in luminance due to yellowing during firing can be suppressed.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have two free valences, An acenaphthene ring, a fluoranthene ring, and a fluorene ring can be mentioned.

Examples of substituents that the divalent hydrocarbon group may have include an alkoxy group, a halogen atom, and a carboxy group.

The alkali-soluble resin (c-1) may further contain other repeating units.
Other repeating units are represented by the following general formula (II) from the viewpoint of forming a hydrogen bond with the phthalocyanine compound (1) and improving the curability when producing a color filter with an ethylenic double bond. is preferred.

In formula (II), ^R5 represents a hydrogen atom or a methyl group.
^R6 represents a trivalent hydrocarbon group which may have a substituent.
^R7 represents a hydrogen atom or a methyl group.

As the optionally substituted trivalent hydrocarbon group for R ⁶ , those exemplified for R ² can be preferably applied. When R ⁶ contains an aromatic ring, it is not included in the repeating unit containing an aromatic ring, and when R ⁶ contains an alicyclic structure, it is not included in the repeating unit containing an alicyclic structure.

In addition, as other repeating units, repeating units represented by the following general formula (III) are preferable from the viewpoint of suppressing yellowing during baking in the color filter production process.

In formula (III), ^R8 represents a hydrogen atom or a methyl group.
^R9 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

( ^R9 )
In formula (III), ^R9 represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent. The monovalent hydrocarbon group includes a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon ring group. When R ⁹ contains an aromatic ring, it is not included in the repeating unit containing an aromatic ring, and when R ⁹ contains an alicyclic structure, it is not included in the repeating unit containing an alicyclic structure.

Examples of the monovalent aliphatic hydrocarbon group include straight-chain aliphatic hydrocarbon groups, branched-chain aliphatic hydrocarbon groups, cyclic aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups combining them. be done.
The number of carbon atoms in the monovalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, even more preferably 5 or more, particularly preferably 7 or more, and 20 or less. It is preferably 18 or less, more preferably 15 or less, and particularly preferably 12 or less. When it is at least the above lower limit, yellowing during baking in the color filter manufacturing process tends to be suppressed, and when it is at most the above upper limit, alkali developability tends to improve when manufacturing the color filter. The above upper and lower limits can be combined arbitrarily. For example, 1 to 20 are preferred, 2 to 20 are more preferred, 3 to 18 are even more preferred, 5 to 15 are even more preferred, and 7 to 12 are particularly preferred.
Specific examples of monovalent aliphatic hydrocarbon groups include, for example, a methyl group, an ethyl group, a tetrahydrodicyclopentadienyl group, and a cyclohexyl group. Among these, a methyl group or a tetrahydrodicyclopentadienyl group is preferable from the viewpoint of suppressing yellowing due to heat.

Although the number of carbon atoms in the monovalent aromatic hydrocarbon group is not particularly limited, it is preferably 6 or more, and preferably 12 or less. For example, 6-12 is preferred. When it is at least the above lower limit, there is a tendency to promote the π-π interaction with the phthalocyanine compound (1), and when it is at most the above upper limit, luminance decreases due to yellowing during firing in the color filter manufacturing process. tends to be suppressed.

The aromatic hydrocarbon ring in the monovalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have one free valence, An acenaphthene ring, a fluoranthene ring, and a fluorene ring can be mentioned.

Examples of substituents that the monovalent hydrocarbon group may have include an alkoxy group, an aryloxy group, and a halogen atom.

When the alkali-soluble resin (c-1) contains repeating units represented by formula (I), the content is not particularly limited, but the total number of moles of the repeating units in the alkali-soluble resin (c-1) is 100. In terms of mol%, it is preferably 15 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 35 mol% or more, and preferably 80 mol% or less, and 70 mol% or less. is more preferable, 60 mol % or less is more preferable, and 50 mol % or less is particularly preferable. When the value is at least the above lower limit, the alkali developability is improved and hydrogen bonds with the phthalocyanine compound (1) tend to be formed strongly. tend to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, 15 to 80 mol% is preferred, 20 to 70 mol% is more preferred, 30 to 60 mol% is even more preferred, and 35 to 50 mol% is particularly preferred.

When the alkali-soluble resin (c-1) contains repeating units represented by formula (II), the content is not particularly limited, but the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100. When expressed as mol %, it is preferably 5 mol % or more, more preferably 10 mol % or more, still more preferably 12 mol % or more, even more preferably 15 mol % or more, particularly preferably 18 mol % or more, and 45 mol %. % or less, more preferably 40 mol % or less, even more preferably 35 mol % or less, and particularly preferably 30 mol % or less. When the value is at least the above lower limit, the alkali developability is improved and hydrogen bonds with the phthalocyanine compound (1) tend to be formed strongly. tend to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, 5 to 45 mol% is preferred, 10 to 45 mol% is more preferred, 12 to 40 mol% is even more preferred, 15 to 35 mol% is even more preferred, and 18 to 30 mol% is particularly preferred.

When the alkali-soluble resin (c-1) contains repeating units represented by formula (III), the content is not particularly limited, but the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100. When expressed as mol%, it is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% or more, even more preferably 15 mol% or more, even more preferably 20 mol% or more, and 25 mol%. 50 mol % or less is preferable, 45 mol % or less is more preferable, 40 mol % or less is even more preferable, and 35 mol % or less is particularly preferable. When it is at least the above lower limit, yellowing due to thermal decomposition of the resin tends to be suppressed during the production of the color filter, and when it is at most the above upper limit, deterioration of alkali developability tends to be suppressed. . The above upper and lower limits can be combined arbitrarily. For example, 1 to 50 mol% is preferable, 5 to 50 mol% is more preferable, 10 to 45 mol% is more preferable, 15 to 45 mol% is even more preferable, 20 to 40 mol% is particularly preferable, and 25 to 35 mol % is particularly preferred.

The (C) alkali-soluble resin in the colored resin composition of the present invention contains an alkali-soluble resin (c-1), but may further contain another alkali-soluble resin (c-2).
As other alkali-soluble resins (c-2), among those that do not fall under the alkali-soluble resin (c-1), for example, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 8-259876, Japan Japanese Unexamined Patent Publication No. 10-300922, Japanese Unexamined Patent Publication No. 11-140144, Japanese Unexamined Patent Publication No. 11-174224, Japanese Unexamined Patent Publication No. 2000-56118, Japanese Unexamined Patent Publication No. 2003-233179, Japan Known polymer compounds described in Japanese Patent Application Laid-Open No. 2009-053652 can be used. Among them, the following resins (c-2-1) to (c-2-5) are preferred.
(c-2-1): for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, at least part of the epoxy groups of the copolymer are unsaturated monobasic A resin obtained by adding an acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction (hereinafter referred to as "resin (c-2-1)" sometimes.)
(c-2-2) Linear alkali-soluble resin containing a carboxy group in the main chain (hereinafter sometimes referred to as "resin (c-2-2)")
(c-2-3) Resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of the resin (c-2-2) (hereinafter sometimes referred to as "resin (c-2-3)" be.)
(c-2-4) (Meth) acrylic resin (hereinafter sometimes referred to as "resin (c-2-4)")
(c-2-5) Epoxy (meth)acrylate resin having a carboxy group (hereinafter sometimes referred to as "resin (c-2-5)")
Of these, the resin (c-2-1) is particularly preferred.

The resins (c-2-2) to (c-2-5) may be dissolved by an alkaline developer and have solubility to the extent that the intended development processing can be carried out. A resin described in JP-A-2009-025813 as the same item can be preferably employed.

The resin (c-2-1) is a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, and at least part of the epoxy groups of the copolymer are unsaturated It is a resin obtained by adding a basic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction.
One preferred embodiment of the resin (c-2-1) is "a copolymer of 5 to 90 mol% of an epoxy group-containing (meth)acrylate and 10 to 95 mol% of another radically polymerizable monomer. On the other hand, a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups of the copolymer, or a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction. alkali-soluble resin obtained by addition”.

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. Acrylate glycidyl ethers may be mentioned. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates may be used alone or in combination of two or more.

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

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

Among them, the structure represented by the 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 is used. The intensity of pixels formed by

The mono(meth)acrylates having the structure represented by formula (V) may be used singly 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). 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 the structure represented by formula (V).

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

The radically polymerizable monomer other than the mono(meth)acrylate represented by the formula (VI) is not particularly limited, but specific examples include styrene, α- and o- , m-, p-alkyl, nitro, cyano, amide, ester derivatives and other vinyl aromatics; butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene and other dienes; methyl (meth)acrylate, (meth) Ethyl acrylate, (meth)acrylate-n-propyl, (meth)acrylate-iso-propyl, (meth)acrylate-n-butyl, (meth)acrylate-sec-butyl, (meth)acrylate- tert-butyl, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, ( meth)dodecyl 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)acrylic salicyl acid, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, (meth)acrylic 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 (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 compounds such as vinyl acetate; 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)acryloylphthalimide is 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 any repeating unit derived from styrene, benzyl (meth)acrylate, or monomaleimide is included in the copolymer of epoxy group-containing (meth)acrylate and other radically polymerizable monomer, other radical polymerization Among the repeating units derived from a styrene monomer, the total content of repeating units derived from styrene, repeating units derived from benzyl (meth)acrylate, and 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 between the epoxy group-containing (meth)acrylate and other radically polymerizable monomers. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and commonly used organic solvents can be used.
Solvents used in the solution polymerization method include, for example, ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve 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 and 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; , xylene, octane, hydrocarbons such as decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactate esters such as methyl lactate, ethyl lactate, butyl lactate; dimethylformamide, N- and 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 mass, more preferably 50 to 800 parts by mass, per 100 parts by mass of the resulting copolymer. By setting the amount of the solvent to be used within the above range, there is a tendency that the molecular weight of the copolymer can be easily controlled.

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. . Organic peroxide catalysts include catalysts classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Examples of radical polymerization initiators 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-isopropyl hydroperoxide, t-butyl hydroperoxide, 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-butylperoxide) oxy)3,3,5-trimethylcyclohexane and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.
Examples of azo compound catalysts 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 usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass 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 heating the mixture while stirring, or by adding the radical polymerization initiator to the monomers. Alternatively, a radical polymerization initiator may be added to the solvent and then the monomer may be added dropwise to the solvent.
Reaction conditions can be set according to the target molecular weight.

In the present invention, as a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, 5 repeating units derived from the epoxy group-containing (meth)acrylate among the total repeating units of the copolymer 90 mol% and 10 to 95 mol% of repeating units derived from other radically polymerizable monomers are preferred; More preferably, 80 to 20 mol% of repeating units derived from a radically polymerizable monomer; 30 to 70 mol% of repeating units derived from an epoxy group-containing (meth)acrylate and another radically polymerizable monomer. Especially preferred is one comprising 70 to 30 mol % of repeating units derived from.

By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth)acrylate to the 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 lower limit or more, heat resistance and strength tend to be sufficient.

The resin (c-2-1) comprises an epoxy resin-containing (meth)acrylate and an epoxy group of a copolymer of another radically polymerizable monomer, an unsaturated monobasic acid (polymerizable component), It is reacted with a basic acid anhydride (alkali-soluble component).
As the unsaturated monobasic acid to be added to the epoxy group, a known unsaturated monobasic acid can be used, and examples thereof include 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.

Polymerizability can be imparted to the resin (c-2-1) by adding the unsaturated monobasic acid to the epoxy group.
The unsaturated monobasic acid is usually 10 to 100 mol%, preferably 10 to 100 mol%, when the total epoxy groups of the copolymer of the epoxy resin-containing (meth)acrylate and other radically polymerizable monomer are 100 mol%. Add 30 to 100 mol %, more preferably 50 to 100 mol %. By making it more than the said lower limit, there exists a tendency for the aging stability of a colored resin composition to become favorable.
A known method can be employed as a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer.

Furthermore, known polybasic acid anhydrides can be used as the polybasic acid anhydride to be added to the hydroxyl group produced when the unsaturated monobasic acid is added to the epoxy group of the copolymer.
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; Anhydrides of tribasic or higher acids such as acids, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride can be mentioned. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

Alkali solubility can be imparted to the resin (c-2-1) by adding the polybasic acid anhydride to the hydroxyl groups generated when the unsaturated monobasic acid is added to the epoxy groups of the copolymer. .
The polybasic acid anhydride is usually 10 to 100 mol%, preferably 20 to 90 mol%, when the total hydroxyl groups generated by adding unsaturated monobasic acid to the epoxy groups of the copolymer are 100 mol%. , more preferably 30 to 80 mol %. When the content is equal to or less than the above upper limit, there is a tendency that the residual film ratio during development becomes favorable, and when the content is equal to or more than the above lower limit, there is a tendency that the solubility becomes sufficient.
A known method can be employed as a method for adding a polybasic acid anhydride to a hydroxyl group produced by adding an unsaturated monobasic acid to an epoxy group of the copolymer.

In order to improve photosensitivity, after adding a polybasic acid anhydride, a glycidyl ether compound having a glycidyl (meth) acrylate or a polymerizable unsaturated group may be added to a part of the generated carboxy groups.
In order to improve developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to some of the generated carboxy groups.
These may be added singly or in combination of two or more.

Examples of glycidyl ether compounds having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group.
Commercially available products include, for example, Nagase ChemteX Co., Ltd. trade names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", " Denacol EX-171” and “Denacol EX-192”.

The structure of the resin (c-2-1) is described, for example, in JP-A-8-297366 and JP-A-2001-89533.

The polystyrene-equivalent weight-average molecular weight of the resin (c-2-1) measured by GPC is not particularly limited, but is preferably 3,000 or more, particularly preferably 5,000 or more. 100,000 or less is preferable, and 50,000 or less is particularly preferable. The above upper and lower limits can be combined arbitrarily. For example, 3,000 to 100,000 is preferred, and 5,000 to 50,000 is particularly preferred. When the content is at least the above lower limit, heat resistance and film strength tend to be improved, and when the content is at most the above upper limit, solubility in a developing solution tends to be improved.
As a measure of the molecular weight distribution, the ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight of the resin (c-2-1) is preferably 2.0 to 5.0.

From the viewpoint of the coating film curability at the time of ultraviolet exposure, among the resins (c-2-4), (c1) an acrylic copolymer resin having an ethylenically unsaturated group in the side chain (hereinafter referred to as (c1) acrylic copolymer resin ) is preferred.
(c1) The partial structure containing a side chain having an ethylenically unsaturated group, which the acrylic copolymer resin has, is not particularly limited, but from the viewpoint of compatibility between coating film curability during ultraviolet exposure and alkali solubility during alkali development. For example, it preferably has a partial structure represented by the following general formula (I′).

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

Further, among the partial structures represented by formula (I'), partial structures represented by the following general formula (II') are preferable from the viewpoint of sensitivity and alkali developability.

In formula (II'), 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.

A 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. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 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, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are preferred. is more preferred.
These polybasic acids may be used singly or in combination of two or more.

When the (c1) acrylic copolymer resin has a partial structure represented by the formula (I′), the content of the partial structure represented by the formula (I′) contained in the (c1) acrylic copolymer resin is particularly Although not limited, it is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more. , Also preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, most preferably 70 mol% or less . When the content is at least the above lower limit, the coating film curability tends to be improved during exposure to ultraviolet rays, and when the content is at most the above upper limit, the alkali solubility tends to be improved during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I′) contained in (c1) the acrylic copolymer resin is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, and 30 to 85 mol%. is more preferred, 40 to 80 mol % is even more preferred, 50 to 75 mol % is particularly preferred, and 65 to 70 mol % is most preferred.

When the (c1) acrylic copolymer resin has a partial structure represented by the formula (II′), the content of the partial structure represented by the formula (II′) contained in the (c1) acrylic copolymer resin is particularly Although not limited, it is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 65 mol% or more. preferably 95 mol% or less, more preferably 90 mol% or less, even more preferably 85 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. preferable. When the content is at least the above lower limit, the coating film curability tends to be improved during exposure to ultraviolet rays, and when the content is at most the above upper limit, the alkali solubility tends to be improved during alkali development. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I′) contained in (c1) the acrylic copolymer resin is preferably 10 to 95 mol%, more preferably 20 to 90 mol%, and 30 to 85 mol%. is more preferred, 40 to 80 mol % is even more preferred, 50 to 75 mol % is particularly preferred, and 65 to 70 mol % is most preferred.

(c1) When the acrylic copolymer resin contains a partial structure represented by formula (I′), the other partial structure is not particularly limited, but from the viewpoint of alkali solubility during alkali development, for example, the following general It is also preferred to have a partial structure represented by formula (III').

In formula (III'), R ^3' represents a hydrogen atom or a methyl group, R ^4' represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or It represents an optionally substituted alkenyl group.

(R4 ^' )
In formula (III'), R ^4' is an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. show.
Alkyl groups for R ^4′ include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, more 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. Even more preferably, 12 or less is particularly preferable. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-18, still more preferably 3-16, even more preferably 5-14, and particularly preferably 8-12.

Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of developability, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
Substituents that the alkyl group may have include, for example, 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. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

The aromatic ring group for R ^4′ includes monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably 6 to 22 carbon atoms, still 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. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring, such as furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring and imidazole ring. , oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, 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, azulene ring .
From the viewpoint of developability, a benzene ring group and a naphthalene ring group are preferred, and a benzene ring group is more preferred.
Substituents which the aromatic ring group may have include, for example, methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group and epoxy group. , an oligoethylene glycol group, a phenyl group, and a carboxy group. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Alkenyl groups for R ^4′ include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, still 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 alkenyl groups 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, cyclohexenyl group. From the viewpoint of developability, a vinyl group and an allyl group are preferred, and a vinyl group is more preferred.

Substituents that the alkenyl group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxy group. is mentioned. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

R ^4' represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent; from the viewpoint of, an alkyl group or an alkenyl group is preferred, and an alkyl group is more preferred.

(c1) When the acrylic copolymer resin has a partial structure represented by the formula (III'), the content of the partial structure represented by the formula (III') in the (c1) acrylic copolymer resin is not particularly limited. , preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, particularly preferably 20 mol% or more, preferably 70 mol% or less, more preferably 60 mol% or less, 50 mol % or less is more preferable, and 40 mol % or less is particularly preferable. Alkali solubility tends to improve by setting it to the above lower limit or more, and the storage stability of the colored resin composition tends to improve by setting it to the above upper limit or less. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by the formula (III′) in the (c1) acrylic copolymer resin is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 50 mol%. , 20 to 40 mol % are particularly preferred.

(c1) When the acrylic copolymer resin contains a partial structure represented by the formula (I′), the other partial structure included improves the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin (c1). From the standpoint of alkali solubility of the phthalocyanine compound (1), it is preferable that the partial structure represented by the following general formula (IV') is included.

In formula (IV'), R ^5' represents a hydrogen atom or a methyl group, R ^6' represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or represents an optionally substituted alkynyl group, a hydroxy group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group. t represents an integer of 0 to 5;

(R6 ^' )
In formula (IV'), R ^6' is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxy group, a carboxy group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent.
Alkyl groups for R ^6′ include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and 12 or less. is particularly preferred. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-18, still more preferably 3-16, even more preferably 3-14, and particularly preferably 5-12.

Examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. From the viewpoint of heat resistance, a dicyclopentanyl group and a dodecanyl group are preferred, and a dicyclopentanyl group is more preferred.
Substituents that the alkyl group may have include, for example, 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. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Alkenyl groups for R ^6′ include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, still 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 alkenyl groups 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, cyclohexenyl group. A vinyl group and an allyl group are preferred, and a vinyl group is more preferred, from the viewpoint of exposure sensitivity during ultraviolet exposure.

Alkynyl groups for R ^6′ include linear, branched and cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkynyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, still 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 alkynyl groups include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1,4 -pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, and 1-hexyn-6-yl group.

Substituents that the alkynyl group may have include, for example, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group and carboxy group. is mentioned. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Halogen atoms for R ^6′ include, for example, fluorine, chlorine, bromine and iodine atoms. (c1) A fluorine atom is preferable from the viewpoint of the storage stability of the acrylic copolymer resin.

Alkoxy groups for R ^6′ include linear, branched and cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still 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 alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups.

Substituents that the alkoxy group may have include, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxy group. , acryloyl group, and methacryloyl group. A hydroxyl group and an oligoethylene glycol group are preferable from the viewpoint of developability.

The alkylsulfide group for R ^6′ includes linear, branched and cyclic alkylsulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be. The above upper and lower limits can be combined arbitrarily. For example, the alkylsulfide group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 16 carbon atoms, even more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

The alkylsulfide group includes, for example, a methylsulfide group, an ethylsulfide group, a propylsulfide group, and a butylsulfide group. A methylsulfide group and an ethylsulfide group are preferable from the viewpoint of developability.

Examples of substituents that the alkyl group in the alkylsulfide group may have include methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl group, carboxy group, acryloyl group, and methacryloyl group. A hydroxyl group and an oligoethylene glycol group are preferable from the standpoint of developability and an image display device.

R ^6' is an optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkynyl group, hydroxy group, carboxy group, halogen atom, alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkylsulfide group, preferably a hydroxy group or a carboxy group, more preferably a carboxy group, from the viewpoint of developability.

　In formula (IV'), t represents an integer of 0 to 5. From the viewpoint of ease of manufacture, t is preferably 0.

(c1) When the acrylic copolymer resin has a partial structure represented by the formula (IV'), the content ratio of the partial structure represented by the formula (IV') in the (c1) acrylic copolymer resin is not particularly limited. , preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 5 mol% or more, particularly preferably 8 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, 30 mol % or less is more preferable, and 20 mol % or less is particularly preferable. When the content is at least the lower limit, the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin (c1) is improved, and the alkali solubility tends to be improved. The content ratio of the structure tends to increase, and the alkali solubility tends to improve. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by the formula (IV') in the (c1) acrylic copolymer resin is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, and even more preferably 5 to 30 mol%. , 8 to 20 mol % are particularly preferred.

(c1) When the acrylic copolymer resin has a partial structure represented by the formula (I'), the partial structure represented by the following general formula (V') is used as another partial structure to be included from the viewpoint of developability. It is also preferable to have

In formula (V'), R ^7' represents a hydrogen atom or a methyl group.

(c1) When the acrylic copolymer resin has a partial structure represented by the formula (V'), the content of the partial structure represented by the formula (III') in the (c1) acrylic copolymer resin is not particularly limited. , preferably 5 mol % or more, more preferably 10 mol % or more, still more preferably 20 mol % or more, and preferably 80 mol % or less, more preferably 70 mol % or less, further preferably 60 mol % or less. Alkali solubility tends to improve by setting it to the above lower limit or more, and the storage stability of the colored resin composition tends to improve by setting it to the above upper limit or less. The above upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by the formula (III') in the (c1) acrylic copolymer resin is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

(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, still more preferably 40 mgKOH/g or more, even more preferably 50 mgKOH/g or more, and 60 mgKOH/g. 300 mgKOH/g or less is preferable, 250 mgKOH/g or less is more preferable, 200 mgKOH/g or less is still more preferable, and 150 mgKOH/g or less is even more preferable. Alkali solubility tends to improve by setting it to the above lower limit or more, and the storage stability of the colored resin composition tends to improve by setting it to the above upper limit or less. The above upper and lower limits can be combined arbitrarily. For example, the acid value of (C) the alkali-soluble resin is preferably 10 to 300 mgKOH/g, more preferably 30 to 300 mgKOH/g, still more preferably 40 to 250 mgKOH/g, even more preferably 50 to 200 mgKOH/g, and 60 to 150 mg KOH/g is particularly preferred.

(C) The weight average molecular weight of the alkali-soluble resin is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 4000 or more, even more preferably 6000 or more, even more preferably 7000 or more, and particularly preferably It is 8,000 or more, preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and particularly preferably 10,000 or less. When the content is at least the above lower limit, heat resistance and coating film curability tend to improve, and when the content is at most the above upper limit, alkali solubility tends to improve. The above upper and lower limits can be combined arbitrarily. For example, (C) the weight average molecular weight of the alkali-soluble resin is preferably 1000 to 30000, more preferably 2000 to 30000, still more preferably 4000 to 20000, even more preferably 6000 to 20000, even more preferably 7000 to 15000, particularly preferably 8000 to 10,000 is particularly preferred.

The content of (C) the alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but the total solid content of the colored resin composition is preferably 1% by mass or more, more preferably 5% by mass or more, and further Preferably 10% by mass or more, more preferably 20% by mass or more, 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. Below, more preferably 50% by mass or less, particularly preferably 40% by mass or less. By setting the thickness to the above lower limit or more, a firm film can be obtained, and there is a tendency that the adhesion to the substrate is excellent. In addition, by making it equal to or less than the above upper limit, there is a tendency that the penetration of the developing solution into the exposed portion is low, and deterioration of the surface smoothness and sensitivity of the pixel can be suppressed. The above upper and lower limits can be combined arbitrarily. For example, the content of (C) alkali-soluble resin in the colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 80% by mass, in the total solid content of the colored resin composition, 10 to 60% by mass. is more preferable, 20 to 60% by mass is even more preferable, 25 to 50% by mass is particularly preferable, and 30 to 40% by mass is particularly preferable.

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

Examples of photopolymerization initiators include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and JP-A-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, etc. radical activators, α-aminoalkylphenone compounds, and oxime ester initiators described in Japanese Patent Application Laid-Open 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 -ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and other halomethylated triazine derivatives;

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 halomethylated oxadiazole derivatives such as ,4-oxadiazole;
2-(2′-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-chlorophenyl)-4,5-bis(3′-methoxyphenyl)imidazole dimer, 2-( 2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (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, and 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-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, Dicyclopentagenyl-Ti-2,6-dipurorophen-1-yl, Dicyclopentagenyl-Ti-2,4-difluorophen-1-yl, Dimethylcyclopentagenyl-Ti-bis-2,3 ,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadienyl-Ti-2,6-difluoro- titanocene derivatives such as 3-(pyrr-1-yl)-phenyl-1-yl;

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-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 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- oxime ester compounds such as yl]-1-(O-acetyloxime);

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 light, 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. , and it is possible to design a highly sensitive colored resin composition in a small amount. In particular, an oxime ester compound having a carbazole ring which may have a substituent is preferable from the viewpoint of light absorption with respect to the i-line (365 nm) of the exposure light source.

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 optionally substituted alkyl group, or an optionally substituted aromatic ring group.
R ^21b represents any substituent containing an aromatic or heteroaromatic ring.
R ^22a represents an optionally substituted alkanoyl group or an optionally substituted aroyl group.

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

The aromatic ring group for R ^21a includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Although the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in the colored resin composition. 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 combined arbitrarily. For example, the aromatic ring group preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 5 to 12 carbon atoms, and particularly preferably 5 to 8 carbon atoms.

Examples of aromatic ring groups include phenyl, naphthyl, pyridyl, furyl, and fluorenyl groups. 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, for example, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted alkoxy group, a carboxy group, a halogen atom, An amino group, an amido group, and an alkyl group can be mentioned. A hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable from the viewpoint of developability. Examples of substituents in the optionally substituted alkyl group and the optionally substituted alkoxy group include a hydroxyl group, an alkoxy group, a halogen atom, and a nitro group. From the viewpoint of developability, R ^21a is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and still more preferably a methyl group.

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

Substituents that the carbazolyl group may have include, for example, 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; 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; a heteroaroyl group which may be substituted; and a thenoyl group which may have a substituent.

Although the number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, it is preferably 2 or more, more preferably 3 or more, preferably 20 or less, more preferably 15 or less, and further preferably 2 or more, more preferably 3 or more, from the viewpoint of solvent solubility and sensitivity. It is preferably 10 or less, particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the alkanoyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 10 carbon atoms, even more preferably 2 to 5 carbon atoms, and particularly preferably 3 to 5 carbon atoms.
Alkanoyl groups include, for example, an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of substituents that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group. is preferred.

Although the number of carbon atoms in the aroyl group in R ^22a is not particularly limited, it is preferably 7 or more, more preferably 8 or more, preferably 20 or less, more preferably 15 or less, and further preferably 7 or more, more preferably 8 or more, from the viewpoint of solvent solubility and sensitivity. It is preferably 10 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the aroyl group is preferably 7-20, more preferably 7-15, even more preferably 7-10, and particularly preferably 8-10.
The aroyl group includes, for example, a benzoyl group and a naphthoyl group.
Substituents that the aroyl group may have include, for example, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. 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 with respect to the i-line (365 nm) of the exposure light source. be done.

In formulas (I-2) and (I-3), R ^21a and R ^22a are the same as in formula (I-1).
R ^23a represents an optionally substituted alkyl group.
R ^24a represents an optionally substituted alkyl group, an optionally substituted aroyl group, an optionally substituted heteroaroyl group, or a nitro group.
The benzene ring constituting the carbazole ring may be further condensed 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 a solvent, it is preferably 1 or more, more preferably 2 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably It is 10 or less, particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-15, even more preferably 1-10, even more preferably 1-5, and particularly preferably 2-5.
Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl groups.
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 preferably unsubstituted.
R ^23a is more preferably an ethyl group from the viewpoint of solubility in solvents and ease of synthesis.

The number of carbon atoms in the alkyl group in R ^24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 1 or more, more preferably 2 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably It is 10 or less, particularly preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group is preferably 1-20, more preferably 1-15, even more preferably 1-10, even more preferably 1-5, and particularly preferably 2-5.
Examples of alkyl groups include methyl, ethyl, propyl, butyl, and cyclohexyl groups.
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 preferably unsubstituted.

The number of carbon atoms in the aroyl group in R ^24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 7 or more, more preferably 8 or more, still more preferably 9 or more, and more preferably 20 or less, and more preferably It is 15 or less, more preferably 10 or less, and particularly preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the aroyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15 carbon atoms, still more preferably 9 to 10 carbon atoms, and particularly preferably 9 carbon atoms.
The aroyl group includes, for example, a benzoyl group and a naphthoyl group.
Substituents that the aroyl group may have include, for example, 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 preferably an ethyl group.

The number of carbon atoms in the heteroaroyl group in R ^24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is preferably 7 or more, more preferably 8 or more, still more preferably 9 or more, and more preferably 20 or less, more preferably It is 15 or less, more preferably 10 or less, and particularly preferably 9 or less. The above upper and lower limits can be combined arbitrarily. For example, the heteroaroyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15 carbon atoms, still more preferably 9 to 10 carbon atoms, and particularly preferably 9 carbon atoms.
Heteroaryl groups include, for example, fluorobenzoyl, chlorobenzoyl, bromobenzoyl, fluoronaphthoyl, chloronaphthoyl, and bromonaphthoyl groups.
Examples of substituents that the heteroaroyl 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 preferably unsubstituted.
From the viewpoint of sensitivity, R ^24a is preferably an optionally substituted aroyl group, more preferably a benzoyl group.

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

Commercial products of oxime ester compounds include, for example, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou Power 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 singly or in combination of two or more.

(D) In addition to the photopolymerization initiator, a chain transfer agent may be used. A chain transfer agent is a compound that has the function of receiving a generated radical and transferring the received radical to another compound.
As the chain transfer agent, various chain transfer agents can be used as long as they are compounds having the above functions. Examples include mercapto group-containing compounds 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 probably because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. Effective in improving sensitivity and surface curability.

Mercapto group-containing compounds include, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, Mercapto group-containing compounds having an aromatic ring such as β-mercaptonaphthalene and 1,4-dimethylmercaptobenzene; 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 -triazine-2,4,6(1H,3H,5H)-trione and other aliphatic mercapto group-containing compounds. A compound having a plurality of mercapto groups is preferable from the viewpoint of surface smoothness.

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, and trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), pionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyl oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate ) is more preferred.
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 of (D) the photopolymerization initiator is not particularly limited, preferably 1% by mass or more in the total solid content of the colored resin composition, more preferably 2% by mass or more, 3% by mass or more is more preferable, 4% by mass or more is particularly preferable, 15% by mass or less is preferable, 10% by mass or less is more preferable, 8% by mass or less is more preferable, and 6% by mass or less is particularly preferable. When the amount is at least the lower limit, the patterning properties after development tend to be ensured, and when the amount is at most the upper limit, a decrease in transmittance due to excessive addition of the photopolymerization initiator tends to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content of the photopolymerization initiator (D) is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, in the total solid content of the colored resin composition, 3 to 8 % by mass is more preferred, and 4 to 6% by mass is particularly preferred.
When the colored resin composition of the present invention contains a chain transfer agent, the content is not particularly limited, but preferably 0.1% by mass or more in the total solid content of the colored resin composition, 0.2% by mass or more is more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and 1 % by mass or less is particularly preferred. When the content is at least the lower limit, the solvent resistance tends to be improved, and when the content is at most the upper limit, the storage stability tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, when the colored resin composition contains a chain transfer agent, the content is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, in the total solid content of the colored resin composition. , more preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1% by mass.

[1-5] (E) Photopolymerizable monomer (E) Photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular-weight compound, but is capable of addition polymerization having at least one ethylenic double bond Compounds (hereinafter referred to as "ethylenic compounds") are preferred. The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with actinic rays, it undergoes addition polymerization and cures due to the action of a photopolymerization initiator. In addition, the monomer in the present invention means a concept corresponding to a so-called polymer substance, and means a concept including dimers, trimers, and oligomers in addition to monomers in a narrow sense.
In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 4 or more, still more preferably 5 or more, and The number is preferably 8 or less, more preferably 7 or less. When the content is at least the lower limit, the sensitivity tends to be high, and when the content is at or below the upper limit, the solubility in a solvent tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, the number of ethylenic double bonds possessed by the polyfunctional ethylenic monomer is preferably 2-8, more preferably 2-7, still more preferably 4-7, and particularly preferably 5-7.

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, esters obtained by esterification reaction with unsaturated carboxylic acids and polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polyisocyanate compounds and (meth)acryloyl An ethylenic compound having a urethane skeleton reacted with a containing hydroxy compound can be mentioned.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid moiety of these acrylates may be replaced with a methacrylic acid ester, an itaconic acid ester with an itaconic acid moiety, a crotonic acid ester with a crotonic acid moiety, or a maleic acid moiety with a maleic acid moiety. esters.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, and 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 glycerol. is mentioned.

Examples of ethylenic compounds 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 and isophorone diisocyanate; Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, Examples include reaction products with (meth)acryloyl group-containing hydroxy compounds such as hydroxy(1,1,1-trimethacryloyloxymethyl)propane.

Other examples of the ethylenic compound used in the present invention include 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 number. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to convert the acid group. Polyfunctional monomers are preferred, and in this ester, polyfunctional monomers in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol are particularly preferred.

One of these monomers may be used alone, but since it is difficult to use a single compound in terms of production, two or more of them may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as a monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When it is at least the above lower limit, there is a tendency that development dissolution characteristics can be improved, and when it is at most the above upper limit, production and handling are improved, and photopolymerization performance, surface smoothness of pixels, etc. are improved. Curability tends to be improved. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when polyfunctional monomers having no acid groups are used in combination, the acid groups of the entire polyfunctional monomer should be adjusted to fall within the above range. is preferred.

In the present invention, the polyfunctional monomer having a more preferable acid group is mainly succinic acid esters of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate, which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture of ingredients. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Also, polyfunctional monomers described in paragraphs [0056] and [0057] of Japanese Patent Application Laid-Open No. 2013-140346 can be used.

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

In the colored resin composition of the present invention, the content of (E) the photopolymerizable monomer is not particularly limited, preferably more than 0% by mass, more preferably 5% by mass or more in the total solid content of the colored resin composition, More preferably 10% by mass or more, still 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, still more preferably 50% by mass Below, more preferably 40% by mass or less, particularly preferably 30% by mass or less. When it is at least the above lower limit, the curability of the coating film tends to increase, and when it is at most the above upper limit, the decrease in alkali developability tends to be suppressed. The above upper and lower limits can be combined arbitrarily. For example, (E) the content of the photopolymerizable monomer, in the total solid content of the colored resin composition, preferably more than 0% by mass and 70% by mass or less, more preferably 5 to 60% by mass, 10 to 50% by mass More preferably, 15 to 40% by mass is even more preferable, and 20 to 30% by mass is particularly preferable.

[1-6] Other Solids The colored resin composition of the present invention can further contain solids other than the above components, if necessary. Such components include, for example, dispersants, dispersing aids, surfactants, and antioxidants.

[1-6-1] Dispersant, Dispersing Aid When the colored resin composition of the present invention contains a pigment as (A) the colorant, it preferably contains a dispersant for the purpose of stably dispersing the pigment. Among the dispersants, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.
Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. Mention may be made of system dispersants. Examples of these dispersing agents include trade names of EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark, manufactured by Lubrizol). (manufactured by Shin-Etsu Chemical Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and dispersants described in Japanese Patent Application Laid-Open No. 2013-119568.

Among polymeric dispersants, block copolymers having functional groups containing nitrogen atoms are preferred, and acrylic block copolymers are more preferred, from the viewpoint of dispersibility and storage stability.
A block copolymer having a functional group containing a nitrogen atom includes an A block having a quaternary ammonium base and/or an amino group in a side chain and a B block having no quaternary ammonium base and/or an amino group. AB block copolymers and/or BAB block copolymers are preferred.

Examples of the functional group containing a nitrogen atom include primary to tertiary amino groups and quaternary ammonium bases, and from the viewpoint of dispersibility and storage stability, it preferably has a primary to tertiary amino group, and a tertiary amino group. It is more preferable to have a group.
The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, it is preferably a repeating unit represented by the following general formula (F1). .

In formula (F1) above, each of R ¹ and R ² is independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted and R ¹ and R ² may combine to form a cyclic structure. ^R3 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 the formula (F1) is not particularly limited, but is preferably 1 or more, preferably 10 or less, and 6 or less. More preferably, 4 or less is even more preferable. For example, 1 to 10 are preferred, 1 to 6 are more preferred, and 1 to 4 are even more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, and methyl, ethyl, propyl, butyl, pentyl and hexyl groups. group is preferred, and methyl group, ethyl group, propyl group and butyl group are more preferred. The alkyl group in formula (F1) above may be linear or branched. The alkyl group in formula (F1) above may contain a cyclic structure such as a cyclohexyl group and a methylcyclohexyl group.

The number of carbon atoms in the optionally substituted aryl group in R ¹ and R ² in the above formula (F1) is not particularly limited, but is preferably 6 or more, preferably 16 or less, and 12 or less. More preferably, 8 or less is even more preferable. For example, 6 to 16 are preferred, 6 to 12 are more preferred, and 6 to 8 are even more preferred. Examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group and anthracenyl group, and phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferred, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferred.

The number of carbon atoms in the optionally substituted aralkyl group in R ¹ and R ² in the formula (F1) is not particularly limited, but is preferably 7 or more, preferably 16 or less, and 12 or less. More preferably, 9 or less is even more preferable. For example, 7 to 16 are preferred, 7 to 12 are more preferred, and 7 to 9 are even more preferred. The aralkyl group includes, for example, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group and a phenylisopropyl group, preferably a phenylmethyl group, a phenylethyl group, a phenylpropyl group and a phenylbutyl group. A phenylethyl group is more preferred.

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

Examples of substituents that the alkyl group, aralkyl group or aryl group in R ¹ and R ² of the above formula (F1) may have include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group. From the viewpoint of ease, it is preferably unsubstituted.

In the above formula (F1), the cyclic structure formed by bonding R ¹ and R ² together includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of these. be done. The nitrogen-containing heterocyclic ring is preferably non-aromatic, and more preferably saturated. Specifically, for example, a nitrogen-containing heterocycle represented by the following formula (F4) is included.

The cyclic structure of formula (F4) above may further have a substituent.

In the above formula (F1), the divalent linking group X includes, 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 ( However, 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 -COO-R ¹⁴ - group.

The content of the repeating unit represented by the formula (F1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more, and further preferably 10 mol% or more. More preferably 15 mol% or more, particularly preferably 20% or more, most preferably 25 mol% or more, preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, and 40 mol % or less is particularly preferred. The above upper limit and lower limit can be combined arbitrarily. For example, the content of the repeating unit represented by the formula (F1) in the total repeating units of the block copolymer is preferably 1 to 90 mol%, more preferably 5 to 90 mol%, and 10 to 70 mol. % is more preferred, 15 to 70 mol % is even more preferred, 20 to 50 mol % is particularly preferred, and 25 to 40 mol % is most preferred. Within the above range, there is a tendency that both dispersion stability and high brightness can be achieved.

The block copolymer preferably has a repeating unit represented by the following formula (F2) from the viewpoint of enhancing compatibility with a binder component such as a solvent and improving dispersion stability.

In formula (F2) above, R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an optionally substituted alkyl group, 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 (F2) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, and 6 or less. is more preferred, and 4 or less is even more preferred. The above upper and lower limits can be combined arbitrarily. For example, the number of carbon atoms in the alkyl group for R ¹¹ in formula (F2) is preferably 1-10, more preferably 1-6, and even more preferably 2-4.
Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, and methyl, ethyl, propyl, butyl, pentyl and hexyl groups. group is preferred, and methyl group, ethyl group, propyl group and butyl group are more preferred.
The alkyl group for R ¹¹ in formula (F2) above may be linear or branched.
The alkyl group for R ¹¹ in formula (F2) may contain a cyclic structure such as a cyclohexyl group and a methylcyclohexyl group.
Examples of the substituent that the alkyl group in R ¹¹ of the above formula (F2) may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. Preferably.

n in the above formula (F2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent, It is more preferably 5 or less. The above upper and lower limits can be combined arbitrarily. For example, 1 to 10 are preferred, 1 to 5 are more preferred, and 2 to 5 are even more preferred.

The content of the repeating unit represented by the formula (F2) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and further preferably 4 mol% or more. Also, it is preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less. The above upper limit and lower limit can be combined arbitrarily. For example, the content of the repeating unit represented by the formula (F2) in the total repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol. % is more preferred. Within the above range, there is a tendency that compatibility with a binder component such as a solvent and dispersion stability can both be achieved.

In addition, the block copolymer preferably has a repeating unit represented by the following formula (F3) from the viewpoint of enhancing compatibility with a binder component such as a solvent and improving dispersion stability.

In formula (F3) above, R ⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. ^R9 is a hydrogen atom or a methyl group.

Although the number of carbon atoms in the optionally substituted alkyl group in R ⁸ of formula (F3) is not particularly limited, it is preferably 1 or more, preferably 10 or less, and more preferably 6 or less. For example, 1 to 10 are preferred, and 1 to 6 are more preferred. Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl groups, and methyl, ethyl, propyl, butyl, pentyl and hexyl groups. group is preferred, and methyl group, ethyl group, propyl group and butyl group are more preferred.
The alkyl group for R ⁸ in formula (F3) above may be linear or branched.
The alkyl group for R ⁸ in formula (F3) above may include a cyclic structure such as a cyclohexyl group and a cyclohexylmethyl group.

Although the number of carbon atoms in the optionally substituted aryl group in R ⁸ of formula (F3) is not particularly limited, it is preferably 6 or more, preferably 16 or less, and more preferably 12 or less. For example, 6-16 is preferred, and 6-12 is more preferred. Examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group and anthracenyl group, and phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, A diethylphenyl group is preferred, and a phenyl group, a methylphenyl group and an ethylphenyl group are more preferred.

Although the number of carbon atoms in the optionally substituted aralkyl group in R ⁸ of formula (F3) is not particularly limited, it is preferably 7 or more, preferably 16 or less, and more preferably 12 or less. For example, 7-16 is preferred, and 7-12 is more preferred. The aralkyl group includes a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group and a phenylisopropyl group, preferably a phenylmethyl group, a phenylethyl group, a phenylpropyl group and a phenylbutyl group, a phenylmethyl group, A phenylethyl group is more preferred.

From the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethyl 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-like alkyl group represented by R ⁸ includes both straight-chain and branched-chain alkyl groups.

The content of the repeating unit represented by the formula (F3) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, and further preferably 50 mol% or more. Moreover, 80 mol% or less is preferable, and 70 mol% or less is more preferable. The above upper and lower limits can be combined arbitrarily. For example, the content of the repeating unit represented by the formula (F3) in the total repeating units of the block copolymer is preferably 30 to 80 mol%, more preferably 40 to 80 mol%, and 50 to 70 mol. % is more preferred. Within the above range, there is a tendency that both dispersion stability and high brightness can be achieved.

The block copolymer contains repeating units other than the repeating unit represented by the general formula (F1), the repeating unit represented by the general formula (F2), and the repeating unit represented by the general formula (F3). may have. Such repeating units include, for example, styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; and repeating units derived from N-methacryloylmorpholine.

The block copolymer has an A block having a repeating unit represented by the general formula (F1) and a repeating unit represented by the general formula (F1) from the viewpoint of further increasing dispersibility. It is preferably a block copolymer, more preferably an AB block copolymer or a BAB block copolymer. The B block preferably has a repeating unit represented by the general formula (F2) and a repeating unit represented by the general formula (F3).

A repeating unit other than the repeating unit represented by the general formula (F1) may be contained in the A block. Examples of such repeating units include repeating units derived from the aforementioned (meth)acrylic acid ester-based monomers. The content of repeating units other than the repeating unit represented by formula (F1) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %. Most preferably, the A block contains no repeating unit other than the repeating unit represented by formula (F1).

A repeating unit other than the repeating unit represented by the general formula (F2) and the repeating unit represented by the general formula (F3) may be contained in the B block. Such repeating units include, for example, styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; and repeating units derived from N-methacryloylmorpholine. In the B block, the content of repeating units other than the repeating unit represented by the general formula (F2) and the repeating unit represented by the general formula (F3) is preferably 0 to 50 mol%, more preferably 0 to 20 mol %. Most preferably, the B block contains no repeating unit other than the repeating unit represented by the general formula (F2) and the repeating unit represented by the general formula (F3).

From the standpoint of dispersibility, the acid value of the block copolymer is preferably as low as possible, and particularly preferably 0 mgKOH/g.

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

The molecular weight of the block copolymer is preferably in the range of 1000 to 30000 in weight average molecular weight (Mw). When it is within the above range, the dispersion stability is improved, and there is a tendency that dried foreign substances are less likely to occur during application by a slit nozzle method.

The block copolymer can be produced by a known method. For example, the monomer into which each repeating unit is introduced can be produced by living polymerization. As the living polymerization method, for example, Japanese Patent Laid-Open No. 9-62002, Japanese Patent Laid-Open No. 2002-31713, P. Lutz, P.; Masson et al, Polym. Bull. 12, 79 (1984); C. Anderson, G.; D. Andrews et al, Macromolecules, 14, 1601 (1981); Hatada, K.; Ute, et al, Polym. J. 17, 977 (1985), K. Hatada, K.; Ute, et al, Polym. J. 18, 1037 (1986), Koichi Ugi, Koichi Hatada, Kobunshi Kako, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Kobunshi Ronbunshu, 46, 189 (1989), M. Kuroki, T.; Aida, J.; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W.; R. A 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, in the total solid content of the colored resin composition, preferably 0.001 wt% or more, 0.01 wt% 0.1% by mass or more is more preferable, 1% by mass or more is particularly preferable, 25% by mass or less is preferable, 20% by mass or less is more preferable, 15% by mass or less is even more preferable, and 10% by mass % or less is particularly preferred. When the content is at least the above lower limit, dispersibility and storage stability tend to improve. When the content is equal to or less than the above upper limit, electrical reliability and developability tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, the content of the dispersant in the total solid content of the colored resin composition is preferably 0.001 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass. , 1 to 10% by weight are particularly preferred.

When the colored resin composition of the present invention contains a pigment and a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the pigment. is 5 parts by mass or more, 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 or less, More preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content of the dispersant with respect to 100 parts by mass of the pigment is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, even more preferably 10 to 50 parts by mass, and even more preferably 15 to 40 parts by mass. 20 to 30 parts by mass is particularly preferred. By setting it within the above range, there is a tendency that a coloring resin composition having excellent dispersion stability and high brightness can be obtained.

When the colored resin composition of the present invention contains a pigment, it may contain, for example, a pigment derivative as a dispersing aid in order to improve the dispersibility and dispersion stability of the pigment.
Examples of pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, Derivatives of diketopyrrolopyrrole-based and dioxazine-based pigments can be mentioned.
Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonamide group, a quaternary salt of a sulfonamide group, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and an amide group. is bonded to the pigment skeleton via, for example, an alkyl group, an aryl group, or a heterocyclic group, or directly bonded. The substituent is preferably a sulfonamide group, a quaternary salt of a sulfonamide group, or a sulfonic acid group, more preferably a sulfonic acid group.
A single pigment skeleton may be substituted with a plurality of substituents, or a mixture of compounds having different numbers of substitutions may be used.
Specific 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, and quinacridone pigments. , sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

[1-6-2] Surfactant The colored resin composition of the present invention may contain a surfactant, and examples of surfactants include anionic, cationic, nonionic, amphoteric surfactants, etc. Various surfactants can be used, but nonionic surfactants are preferred because 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, preferably 0.001 mass% or more in the total solid content of the colored resin composition, more preferably 0.01% 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, still more preferably 0.5% by mass % by mass or less, particularly preferably 0.3% by mass or less. The above upper and lower limits can be combined arbitrarily. For example, the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and 0.05 to 0.5% by mass in the total solid content of the colored resin composition. is more preferred, and 0.1 to 0.3% by mass is particularly preferred.

[2] Preparation of colored resin composition (A) When preparing a colored resin composition containing a pigment as a coloring agent, for example, each predetermined amount of pigment, solvent and dispersant is weighed, and in a dispersion treatment step, coloring containing pigment A pigment dispersion is prepared by dispersing the agent. As described above, it is preferable to use, for example, a dispersing aid and/or a dispersing resin in combination in the dispersing treatment step.
In the dispersion treatment step, for example, paint conditioners, sand grinders, ball mills, roll mills, stone mills, jet mills and homogenizers can be used. Since the colorant is finely divided by performing this dispersing treatment, the coating property of the colored resin composition is improved, and the transmittance of the pixels in the color filter substrate of the product is improved. When performing dispersion treatment using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm.

The temperature during the dispersion treatment is preferably set in the range of 0°C or higher, more preferably room temperature (eg, 25°C) or higher, and preferably 100°C or lower, preferably 80°C or lower. The above upper and lower limits can be combined arbitrarily. For example, it can be set to 0-100°C, 0-80°C, or room temperature to 80°C. The appropriate dispersion time may vary depending on the composition of the pigment dispersion, the size of the sand grinder, and the like, and may be adjusted as appropriate.

The pigment dispersion obtained in the dispersion treatment step is mixed with a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator and (E) a photopolymerizable monomer, and if necessary, components other than the above. Make a uniform dispersion solution. In addition, in each step of dispersion treatment and mixing, since fine dust may be mixed, it is preferable to filter the obtained pigment dispersion with a filter or the like.

(A) when preparing a colored resin composition containing no pigment as a coloring agent, (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator and (E) A uniform solution can be obtained by mixing a photopolymerizable monomer and, if necessary, components other than those described above. It is preferable to filter the obtained solution with a filter or the like.

The alkali-soluble resin (c-1) having a repeating unit containing an aromatic ring on the side chain contained in the alkali-soluble resin (C) is a resin obtained by polymerizing a monomer mixture containing a monomer containing an aromatic ring. is preferred. Furthermore, it is more preferred that the monomer mixture contains a monomer containing an alicyclic structure. Further, it is more preferable that the alicyclic structure is a saturated alicyclic structure. A resin obtained by polymerizing a monomer mixture containing a (meth)acrylic monomer containing an aromatic ring and a (meth)acrylic monomer containing an alicyclic structure is particularly preferred.

[3] Production of Color Filter Substrate The color filter of the present invention comprises pixels produced using the colored resin composition of the present invention.

[3-1] Transparent substrate (support)
The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly(meth)acryl. A thermosetting resin sheet such as a base resin, or various types of glass may be used. Among these, glass or heat-resistant resin is preferable from the viewpoint of heat resistance.

In order to improve surface physical properties such as adhesion, the transparent substrate and the substrate provided with a black matrix, which will be described later, may be treated with corona discharge treatment, ozone treatment, silane coupling agents, various resins such as urethane resins, if necessary. A thin film forming process or the like may be performed.
The thickness of the transparent 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. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm.
In addition, when thin film formation processing of various resins is performed, the film thickness is preferably in the range of 0.01 μm or more, more preferably 0.05 μm or more, and preferably 10 μm or less, more preferably 5 μm or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm.

[3-2] Black Matrix The color filter of the present invention can be produced by providing a black matrix on a transparent substrate, and more preferably by forming pixel images of red, green and blue. Among red, green, and blue pixels, the colored resin composition of the present invention is preferably used as a coating liquid for forming green pixels (resist pattern). Using a green pixel (resist pattern) forming coating liquid, on a resin black matrix formation surface formed on a transparent substrate, or on a metal black matrix formation surface formed using a chromium compound or other light-shielding metal material, A pixel image is formed by carrying out coating, heat drying, imagewise exposure, development and baking.

A black matrix is formed on a transparent substrate using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, chromium compounds such as chromium metal, chromium oxide, and chromium nitride, alloys of nickel and tungsten, and the like are used.
These metal light-shielding films are generally formed by a sputtering method. After forming a desired film pattern with a positive photoresist, chromium is treated with ceric ammonium nitrate and perchloric acid and/or nitric acid. and other materials are etched using an etchant suitable for the material, and finally the positive photoresist is removed with a special remover to form a black matrix. be able to.

In this case, first, a thin film of these metals or metal/metal oxides is formed on a transparent substrate by vapor deposition, sputtering, or the like. 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 stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a black matrix is formed using a colored resin composition containing a black colorant. For example, black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, and titanium black, or a plurality of black colorants, or inorganic or organic pigments, dyes, red, green, blue, etc. A black matrix can be formed using a colored resin composition containing a mixed black colorant in the same manner as in the method for forming pixel images of red, green and blue below.

[3-3] Formation of pixels On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied, dried, and then a photomask is overlaid on the coating film. A pixel image is formed by imagewise exposure through a photomask, development, and thermal curing or photocuring as necessary. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

The application of the colored resin composition for color filters can be performed by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Above all, according to the die coating method, the amount of coating liquid used is greatly reduced, and there is no effect of mist that adheres when using the spin coating method, and the generation of foreign matter is suppressed. from the point of view.

If the thickness of the coating film is too large, it may become difficult to develop the pattern and it may become difficult to adjust the gap in the process of forming a liquid crystal cell. 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, still more preferably 0.8 μm or more, and preferably 20 μm or less, more preferably 10 μm or less. More preferably, it is in the range of 5 μm or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 0.2 to 20 μm, more preferably 0.5 to 10 μm, still more preferably 0.8 to 5 μm.

[3-4] Drying of Coating Film Drying of the coating film after applying the colored resin composition to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is dried by heating again. Pre-drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature 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 combined arbitrarily. For example, it is preferably 40 to 80°C, more preferably 50 to 70°C. The drying time is preferably 15 seconds or longer, more preferably 30 seconds or longer, and preferably 5 minutes or shorter, more preferably 3 minutes or shorter. The above upper and lower limits can be combined arbitrarily. For example, preferably 15 seconds to 5 minutes, more preferably 30 seconds to 3 minutes.

The temperature conditions for reheating and drying are preferably higher than the pre-drying temperature. More preferably, it is 130° C. or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 50 to 200°C, more preferably 50 to 160°C, still more preferably 70 to 130°C. The drying time depends on the heating temperature, but is preferably 10 seconds or longer, more preferably 15 seconds or longer, and preferably 10 minutes or shorter, more preferably 5 minutes. The above upper and lower limits can be combined arbitrarily. For example, preferably 10 seconds to 10 minutes, more preferably 15 seconds to 5 minutes. The higher the drying temperature, the better the adhesiveness to the transparent substrate. However, if the drying temperature is too high, the alkali-soluble resin may decompose and thermal polymerization may be induced, resulting in defective development. As the drying step of the coating film, a reduced pressure drying method may be used in which the drying is performed in a reduced pressure chamber without raising the temperature.

[3-5] Exposure Step Imagewise exposure is carried out by overlaying a negative matrix pattern on the coating film of the colored resin composition and irradiating it with an ultraviolet or visible light source through this mask pattern. In this case, if necessary, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent deterioration of the sensitivity of the photopolymerizable layer due to oxygen. The light source used for the above image 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, and fluorescent lamps, argon ion lasers, YAG lasers, Examples include laser light sources such as excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating and using the light of a specific wavelength.

[3-6] Development step The color filter of the present invention is formed by subjecting the coating film using the colored resin composition of the present invention to imagewise exposure with the light source described above, followed by an aqueous solution containing a surfactant and an alkaline compound. can be produced by forming an image on the substrate by developing with This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

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, phosphorus Inorganic alkaline compounds such as potassium acid, 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 diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include organic alkaline compounds. These alkaline compounds may be used singly 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; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.

Examples of organic solvents include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. An organic solvent can be used in combination with an aqueous solution.
The conditions for development are not particularly limited, but the development temperature is preferably 10° C. or higher, more preferably 15° C. or higher, still more preferably 20° C. or higher, and preferably 50° C. or lower, more preferably 45° C. or lower. More preferably, the temperature is in the range of 40°C or less. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 10 to 50°C, more preferably 15 to 45°C, still more preferably 20 to 40°C.
The development method can be any one of immersion development, spray development, brush development, ultrasonic development, and the like.

[3-7] Baking The color filter after development is baked. The firing conditions at this time are selected in the range of preferably 100° C. or higher, more preferably 150° C. or higher, and preferably 280° C. or lower, more preferably 250° C. or lower. The above upper and lower limits can be combined arbitrarily. For example, it is preferably 100 to 280°C, more preferably 150 to 250°C. The time is selected in the range of 5 minutes or more and 60 minutes or less. Through a series of these steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. The order of patterning the four colors is not limited to the order described above.

[3-8] Formation of Transparent Electrode The color filter of the present invention is used as a part of a component such as a color display or a liquid crystal display by forming a transparent electrode such as ITO on an image as it is. In order to improve surface smoothness and durability, a topcoat layer of polyamide, polyimide, or the like may be provided on the image, if necessary. In addition, in some applications such as planar alignment driving system (IPS mode), the transparent electrode may not be formed.

[4] Image display device (panel)
An image display device of the present invention includes the color filter of 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 the liquid crystal display device of the present invention will be described. The liquid crystal display device of the present invention is usually manufactured by forming an alignment film on the color filter of the present invention, dispersing spacers on the alignment film, and then bonding it to a counter substrate to form a liquid crystal cell. Inject liquid crystal into the , and connect it to the counter electrode to complete the process. The alignment film is preferably a resin film such as polyimide. A gravure printing method and/or a flexographic printing method is usually employed for forming the alignment film, and the thickness of the alignment film is set to several tens of nanometers. After hardening the alignment film by baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth, so that the surface state is processed so that the inclination of the liquid crystal can be adjusted.

The spacer used has a thickness corresponding to the gap (clearance) with the opposing substrate, and a thickness of 2 to 8 μm is suitable. A photo-spacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

The gap between the opposing substrate and the bonding substrate varies depending on the application of the liquid crystal display device, but is selected in the range of 2 μm or more and 8 μm or less. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
After the liquid crystal cell with its periphery sealed is cut into panels, the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. . The degree of pressure reduction in the liquid crystal cell is preferably 1×10 ⁻² Pa or less, more preferably 1×10 ⁻³ or less, and preferably 1×10 ⁻⁷ Pa or more, more preferably 1×10 ⁻⁶ Pa or more. is. The above upper and lower limits can be combined arbitrarily. It is preferably from 1×10 ^-7 to 1×10 ^-2 Pa, more preferably from 1×10 ^-6 to 1×10 ^-3 Pa. In addition, it is preferable to heat the liquid crystal cell when the pressure is reduced. The above upper bounds and my opinion can be combined arbitrarily. For example, it is preferably 30 to 100°C, more preferably 50 to 90°C.

The heating and holding at the reduced pressure is in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. A liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curing resin.
There is no particular limitation on the type of liquid crystal, and any known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, or the like may be used. Thermotropic liquid crystals include nematic liquid crystals, smestic liquid crystals, cholesteric liquid crystals, and the like, and any of them may be used.

[4-2] Organic EL display device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. A multicolor organic EL element 100 is produced by laminating an organic light-emitting body 500 on a blue color filter formed with an organic protective layer 30 and an inorganic oxide film 40 interposed therebetween.

As a method of stacking the organic light emitter 500, a method of 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, or , a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40, and the like. The organic EL element 100 manufactured in this way can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

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 as long as it does not exceed the gist thereof.

<Phthalocyanine compound A>
A phthalocyanine compound A having the following chemical structure synthesized according to Example 30 of JP-A-05-345861 was used.

<Dispersant A>
A methacrylic AB block copolymer comprising 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 number is 120 mg KOH/g and the acid number is less than 1 mg KOH/g.

The content ratio 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 .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 under nitrogen substitution and heated to 120°C. Here, 38.5 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) are added dropwise, and 2.2'-azobis- A mixed solution of 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.3 parts by mass of trisdimethylaminomethylphenol and 0.06 parts by mass of hydroquinone were added to 11.8 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. After that, 43.6 parts by mass of succinic anhydride (SA) and 1.4 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw of the thus obtained alkali-soluble resin A measured by GPC was about 9000, the acid value was 100 mgKOH/g, and the double bond equivalent was 410 g/mol. Further, when the total number of moles of the repeating units in the alkali-soluble resin A is 100 mol%, the repeating unit containing an aromatic ring on the side chain is 37 mol%, and the repeating unit containing a saturated alicyclic structure on the side chain. is 3 mol %, and the alkali-soluble resin A corresponds to the alkali-soluble resin (c-1).
Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content was 40% by mass, and used as alkali-soluble resin A for the preparation of a colored resin composition.

<Alkali-soluble resin B>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution and heated to 120°C. Here, 38.5 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 6.6 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) are added dropwise, and 2.2'-azobis- A mixed solution of 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.3 parts by mass of trisdimethylaminomethylphenol and 0.06 parts by mass of hydroquinone were added to 11.8 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. After that, 66.3 parts by mass of tetrahydrophthalic anhydride (THPA) and 1.4 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw of the alkali-soluble resin B thus obtained measured by GPC was about 14000, the acid value was 100 mgKOH/g, and the double bond equivalent was 440 g/mol. Further, when the total number of moles of the repeating units in the alkali-soluble resin B is 100 mol%, the repeating unit containing an aromatic ring on the side chain is 37 mol%, and the repeating unit containing a saturated alicyclic structure on the side chain. is 3 mol %, and the alkali-soluble resin B corresponds to the alkali-soluble resin (c-1).
Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content was 40% by mass, and used as alkali-soluble resin B for the preparation of a colored resin composition.

<Alkali-soluble resin C>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution and heated to 120°C. Here, 10.4 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66.0 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise, and 2.2'-azobis- A mixed solution of 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.3 parts by mass of trisdimethylaminomethylphenol and 0.06 parts by mass of hydroquinone were added to 15.1 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. After that, 59.3 parts by mass of tetrahydrophthalic anhydride (THPA) and 1.4 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw of the alkali-soluble resin C thus obtained measured by GPC was about 9000, the acid value was 80 mgKOH/g, and the double bond equivalent was 480 g/mol. Further, when the total number of moles of the repeating units in the alkali-soluble resin C is 100 mol%, the repeating unit containing an aromatic ring on the side chain is 10 mol%, and the repeating unit containing a saturated alicyclic structure on the side chain. is 30 mol %, and the alkali-soluble resin C does not correspond to the alkali-soluble resin (c-1).
Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content was 40% by mass, and used as an alkali-soluble resin C for preparing a colored resin composition.

<Alkali-soluble resin D>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution and heated to 120°C. Here, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, and 4.4 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise to give 2.2′-azobis-2- A mixed solution of 8.47 parts by mass of methylbutyronitrile was added dropwise over 3 hours, and the mixture was further stirred at 90° C. for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 59.8 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. After that, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw of the alkali-soluble resin D thus obtained measured by GPC was about 9000, the acid value was 25 mgKOH/g, and the double bond equivalent was 260 g/mol. Further, when the total number of moles of the repeating units in the alkali-soluble resin D is 100 mol%, the repeating unit containing an aromatic ring on the side chain is 5 mol%, and the repeating unit containing a saturated alicyclic structure on the side chain. is 2 mol %, and the alkali-soluble resin D does not correspond to the alkali-soluble resin (c-1).
Propylene glycol monomethyl ether acetate was added to the obtained resin solution so that the solid content was 40% by mass, and used as alkali-soluble resin D for the preparation of a colored resin composition.

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

On the other hand, 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, and t-butylperoxy-2-ethyl were added to the monomer tank. 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 in a chain transfer tank, and the temperature of the reaction tank was was stabilized at 90° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. The dropping was carried out over 135 minutes while maintaining the temperature at 90°C, and 60 minutes after the dropping was completed, 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 oxygen/nitrogen=5/95 (v/v) mixed gas bubbling 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 charged into the reactor, and the temperature was maintained at 110°C. was reacted for 9 hours.
After cooling to room temperature, an alkali-soluble resin E 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 was obtained as measured by GPC.
When the total number of moles of the repeating units in the alkali-soluble resin E is 100 mol%, the repeating unit containing an aromatic ring on the side chain is 0 mol%, and the repeating unit containing a saturated alicyclic structure on the side chain is 44. mol %, and the alkali-soluble resin E does not correspond to the alkali-soluble resin (c-1).

<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, 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (derived from dispersant A solvent), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours using a paint shaker. After completion of the dispersion, the beads and the dispersion liquid were separated by a filter to prepare a green dye dispersion liquid A.

<Preparation of Green Pigment Dispersion A>
As shown in Table 1, C.I. I. 13.9 parts by mass of Pigment Green 58, 1.9 parts by mass of dispersant A in terms of solid content, 4.2 parts by mass of alkali-soluble resin E in terms of solid content, and 80.0 parts of propylene glycol monomethyl ether acetate as a solvent. Parts by mass (including solvent derived from dispersant A and solvent derived from alkali-soluble resin E) and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled in a stainless steel container and dispersed for 6 hours using a paint shaker. After completion of dispersion, the beads and the dispersion liquid were separated by a filter to prepare a green pigment dispersion liquid A.

<Preparation of yellow pigment dispersion liquid A>
As shown in Table 1, C.I. 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 E 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 E), 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 in a stainless steel container and painted. A dispersion treatment was performed for 6 hours in a shaker. After the dispersion was completed, the beads and the dispersion liquid were separated by a filter to prepare a yellow pigment dispersion liquid A.

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

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

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

<Preparation of colored resin composition>
Each component described in Table 2 was mixed at the solid content ratio described to prepare a colored resin composition. In addition, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used so that the content of the total solid content of the colored resin composition was 15.2% by mass. The mixing ratio (mass ratio) of PGMEA/PGME in the obtained colored resin composition was 90/10.

<Color characteristic evaluation>
On a 50 mm square, 0.5 mm thick glass substrate (AGC, AN100), the above colored resin composition was applied by spin coating, dried under reduced pressure, and then placed on a hot plate at 90° C. for 90 seconds. Prebaked. Then, the entire surface was exposed with a 2 kW high-pressure mercury lamp at an exposure amount of 40 mJ/cm ² and an illuminance of 30 mW/cm ² . After that, baking was performed at 230° C. for 20 minutes in a clean oven to prepare a colored substrate. Using the obtained colored substrate, the transmission spectrum was measured with a C light source using a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the chromaticity (sx, sy) and luminance LY were calculated.

In addition, using the obtained colored substrate, the contrast when the chromaticity of sy = 0.607 was measured with a C light source with a contrast meter (CT-1 manufactured by Tsubosaka Electric Co., Ltd.). Table 2 shows the measured contrast.

As is clear from Table 2, Examples 1 and 2 containing alkali-soluble resin A or B corresponding to alkali-soluble resin (c-1) are Comparative Examples 1-3 that do not contain alkali-soluble resin (c-1). Clearly higher contrast than This is because the alkali-soluble resin (c-1) contains many repeating units containing an aromatic ring on the side chain, and the aromatic ring and the phthalocyanine compound A approach each other by π-π stacking, It is considered that the molecules associate with each other in the baking process, promote regular arrangement (crystallization), and improve the contrast. In addition, it is believed that the small amount of repeating units containing an alicyclic structure on the side chain prevents the bulky alicyclic structure from inhibiting the association of the molecules of the phthalocyanine compound, thereby improving the contrast.

Also, as shown in Reference Examples 1 and 2, C.I. I. When Pigment Green 58 is used, no change in contrast is observed depending on the presence or absence of the alkali-soluble resin (c-1). This fact also supports the mechanism that the alkali-soluble resin (c-1) specifically acts on the phthalocyanine compound (1) to improve the contrast.

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

REFERENCE SIGNS LIST 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

A colored resin composition containing (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and (E) a photopolymerizable monomer,
The (A) colorant contains a phthalocyanine compound having a chemical structure represented by the following general formula (1),
The (C) alkali-soluble resin contains an alkali-soluble resin (c-1) having a repeating unit containing an aromatic ring on a side chain,
When the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100 mol%, the total content of repeating units containing an aromatic ring on the side chain is 20 mol% or more. A colored resin composition.

(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), provided that one or more of A 1 to A 16 represents a fluorine atom, and at least one of A 1 to A 16 represents a group represented by the following general formula (2).)

(In Formula (2), X represents a divalent linking group. The benzene ring in Formula (2) may have any substituent. * represents a bond.)
The colored resin composition according to claim 1, wherein the total content of repeating units containing aromatic rings on the side chains in the alkali-soluble resin (c-1) is 30 mol% or more.
The colored resin according to claim 1 or 2, wherein the alkali-soluble resin (c-1) has a repeating unit containing an alicyclic structure on a side chain, and the alicyclic structure is a saturated alicyclic structure. Composition.
The colored resin composition according to claim 3, wherein in the repeating unit containing the alicyclic structure on the side chain, the distance from the main chain to the alicyclic structure is 4 atoms or less.
When the total number of moles of repeating units in the alkali-soluble resin (c-1) is 100 mol%, the total content of repeating units containing an alicyclic structure on the side chain is 10 mol% or less. The colored resin composition according to claim 3 or 4.
The alkali-soluble resin (c-1) has at least one selected from repeating units represented by the following general formulas (3) and (4) as the repeating unit containing an aromatic ring on the side chain. , The colored resin composition according to any one of claims 1 to 5.

(In formulas (3) and (4), R 1 each independently represents a hydrogen atom or a methyl group. The benzene ring in formulas (3) and (4) has an optional substituent. may be used.)
The colored resin composition according to claim 6, wherein the alkali-soluble resin (c-1) has a repeating unit represented by the general formula (3) as a repeating unit containing an aromatic ring on the side chain.
As the repeating unit containing an alicyclic structure on the side chain of the alkali-soluble resin (c-1), at least one selected from repeating units represented by the following general formula (5) and the following general formula (6) Having, the colored resin composition according to any one of claims 3 to 5.

(In formulas (5) and (6), R 1 each independently represents a hydrogen atom or a methyl group. The saturated hydrocarbon rings in formulas (5) and (6) have optional substituents. may be.)
The alkali-soluble resin (c-1) has a repeating unit represented by the general formula (5) as a repeating unit containing an alicyclic structure on the side chain, colored resin composition according to claim 8 .
The colored resin composition according to any one of claims 1 to 9, wherein the alkali-soluble resin (c-1) has a repeating unit represented by the following general formula (I).

(In Formula (I), R 1 and R 3 each independently represent a hydrogen atom or a methyl group.
R 2 represents a trivalent hydrocarbon group which may have a substituent.
R 4 represents a divalent hydrocarbon group which may have a substituent. )
The colored resin composition according to any one of claims 1 to 10, wherein the content of (A) the colorant is 10% by mass or more relative to the total solid content of the colored resin composition.
The colored resin composition according to any one of claims 1 to 11, wherein the content of the alkali-soluble resin (c-1) is 10% by mass or more relative to the total solid content of the colored resin composition.
A color filter comprising pixels produced using the colored resin composition according to any one of claims 1 to 12.
An image display device comprising the color filter according to claim 13.