JP2024040909A - Colored resin composition, color filter, and image display device - Google Patents

Abstract

To provide a colored resin composition capable of realizing a wide color gamut, having high contrast, and excellent in patterning property.SOLUTION: A 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) has a red colorant (a-1) having at least one absorption peak with an absorbance of 1.0 or more at a wavelength of 560 nm or more when measured at a concentration of 10 ppm and a measurement cell length of 1 cm, using water or propylene glycol monomethyl ether acetate as a solvent. The content of the colorant (A) is 30 mass% or more based on the total solid content of the colored resin composition.SELECTED DRAWING: None

Description

The present invention relates to a colored resin composition, a color filter, and an image display device.

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

In recent years, color filters are required to have higher brightness, higher contrast, and a wider color gamut. In particular, in red pixel applications, C.I. Pigment Red 254 and C.I. Pigment Red 177, which have been commonly used up to now, are no longer able to meet the market demand for a wider color gamut, and studies on red colorants with high coloring power have been actively conducted (see, for example, Patent Documents 1 and 2).

Japanese Patent Application Publication No. 2015-79161 Japanese Patent Application Publication No. 2020-197567

The present inventors conducted a study and found that in the colored resin compositions described in Patent Documents 1 and 2, when trying to achieve a wide color gamut, the amount of red colorant added increases, resulting in a decrease in contrast, It has been found that pattern formation becomes difficult.

Therefore, an object of the present invention is to provide a colored resin composition that can realize a wide color gamut, has high contrast, and has excellent patterning properties.

The first invention solves the above problem by using a colored resin composition containing a red colorant having a specific absorption peak wavelength in a solvent.
The first invention has the following aspects.

[1] (A) Colorant, (B) Solvent, (C) Alkali-soluble resin, (D) Photoinitiator,
and (E) a colored resin composition containing a photopolymerizable monomer,
When the colorant (A) is measured using water or propylene glycol monomethyl ether acetate as a solvent at a concentration of 10 ppm and a measurement cell length of 1 cm, the absorbance is 1.
A red colorant (a
-1),
A colored resin composition, wherein the content of the colorant (A) is 30% by mass or more based on the total solid content of the colored resin composition.
[2] The colored resin composition according to [1], wherein the content ratio of the colorant (A) is 50% by mass or less based on the total solid content of the colored resin composition.
[3] The colored resin composition according to [1] or [2], wherein the content of the red colorant (a-1) is 10% by mass or less based on the total amount of the colorant (A).
[4] The colored resin composition according to any one of [1] to [3], wherein the red colorant (a-1) is a dye.
[5] The colored resin composition according to [4], wherein the red colorant (a-1) is a xanthene dye.
[6] The colored resin composition according to any one of [1] to [3], wherein the red colorant (a-1) is a xanthene compound having a chemical structure represented by the following general formula (1). .

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
a represents an integer from 2 to 5.
R ⁵ represents an arbitrary substituent, and a plurality of R ⁵ may be different from each other, two or more of which are monovalent groups having at least one selected from the group consisting of -SO ₂ ^- and -COO ^- represents.
M represents a metal atom.
l, m and n each independently represent an integer from 1 to 5, and l=m×n. )

[7] The colored resin composition according to [6], wherein M in the general formula (1) is an alkaline earth metal atom.
[8] A color filter having pixels made using the colored resin composition according to any one of [1] to [7].
[9] An image display device comprising the color filter according to [8].

The second invention solves the above problem by using a colored resin composition containing a red colorant having a specific absorption peak wavelength in the coating film.
The second invention has the following aspects.

[10] A colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photoinitiator, and (E) a photopolymerizable monomer,
A red colorant in which the colorant (A) exhibits an absorption peak at a wavelength of 560 nm or more when measured on a 2 μm thick coating obtained by coating a colored resin composition on a substrate and baking it at 230° C. for 20 minutes. Contains a colorant (a-2) (excluding C.I. Pigment Red 177),
The content ratio of the red colorant (a-2) is 15% by mass or less based on the total amount of the colorant (A),
A colored resin composition, wherein the content of the colorant (A) is 30% by mass or more based on the total solid content of the colored resin composition.
[11] The content of the colorant (A) is 50% by mass based on the total solid content of the colored resin composition.
The colored resin composition according to [10] below.
[12] The content ratio of the red colorant (a-2) is 10% relative to the total amount of the colorant (A).
% by mass or less, the colored resin composition according to [10] or [11].
[13] The colored resin composition according to any one of [10] to [12], wherein the red colorant (a-2) is a dye.
[14] The colored resin composition according to [13], wherein the red colorant (a-2) is a xanthene dye.
[15] The colored resin composition according to any one of [10] to [12], wherein the red colorant (a-2) is a xanthene compound having a chemical structure represented by the following general formula (1). .

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
a represents an integer from 2 to 5.
R ⁵ represents an arbitrary substituent, and a plurality of R ⁵ may be different from each other, two or more of which are monovalent groups having at least one selected from the group consisting of -SO ₂ ^- and -COO ^- represents.
M represents a metal atom.
l, m and n each independently represent an integer from 1 to 5, and l=m×n. )

[16] The colored resin composition according to [15], wherein M in the general formula (1) is an alkaline earth metal atom.
[17] A color filter having pixels formed using the colored resin composition according to any one of [10] to [16].
[18] An image display device having the color filter according to [17].

According to the present invention, it is possible to provide a colored resin composition that can achieve a wide color gamut, has high contrast, and has excellent patterning properties.

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

Embodiments of the present invention will be specifically described below. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist.

As described above, the present invention includes the first invention and the second invention. The first invention and the second invention are referred to as the "present invention".
In the present invention, the term "weight average molecular weight" refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In the present invention, "total solid content" shall mean all components other than the solvent in the colored resin composition. Even if components other than the solvent are liquid at room temperature, those components are not included in the solvent.
Include in total solids.
In the present invention, the "amine value" refers to the amine value in terms of effective solid content unless otherwise specified, and is a value expressed by the amount of base and the mass of KOH equivalent to 1 g of solid content of the dispersant.
In the present invention, "C.I." means color index.
In the present invention, the red colorant means a colorant having a maximum absorption wavelength in the range of 450 to 600 nm.

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

[1-1] (A) Colorant As the first invention, the colorant (A) contained in the colored resin composition uses water or propylene glycol monomethyl ether acetate as a solvent, has a concentration of 10 ppm, and has a measurement cell length of 1 cm. Contains a red colorant (a-1) that has at least one absorption peak with an absorbance of 1.0 or more at a wavelength of 560 nm or more when measured at .
In the colored resin composition of the present invention, since the colorant (A) contains the red colorant (a-1), the amount of the colorant (A) required to reproduce the desired color is reduced, Since components such as (C) alkali-soluble resin that contribute to patterning properties increase, patterning properties tend to improve.
In addition, in order to reproduce the desired color, the ratio of the colorant corresponding to red colorant (a-1) in the colorant (A) can be lowered, so in order to have relatively good contrast. C.I., which is preferably used as a general-purpose red colorant. I. Pigment Red 177 and C. I
．． The ratio of Pigment Red 254 can be increased, and the contrast tends to be good.

In addition, as a second invention, the coloring agent (A) contained in the colored resin composition is prepared by coating the colored resin composition on a substrate so that the resulting coating film has a thickness of 2 μm, and heating it at 230° C. for 20 minutes. A red colorant (a
-2) (excluding C.I. Pigment Red 177).
In the colored resin composition of the present invention, since the colorant (A) contains the red colorant (a-2), the amount of the colorant (A) required to reproduce the desired color is reduced, Since components such as (C) alkali-soluble resin that contribute to patterning properties increase, patterning properties tend to improve.

For coating and baking the colored resin composition, the method described in [3] Manufacture of color filter substrate, which will be described later, can be used. Furthermore, for the measurement of the absorption peak, the method described in <Measurement of color characteristics> below can be used.

[1-1-1] Red colorant (a-1)
Examples of the colorant corresponding to the red colorant (a-1) include C.I. I. acid red 5
2 and its derivatives.

The content of the red colorant (a-1) is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, based on the total amount of the (A) colorant. Moreover, it is preferably 15% by mass or less, and more preferably 10% by mass or less. When the content is equal to or more than the lower limit value, the coloring power tends to increase and a wide color gamut can be supported, and when it is equal to or less than the upper limit value, the contrast tends to increase.

The content ratio of the colorant (A) is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more based on the total solid content of the colored resin composition. 60 again
It is preferably at most 50% by mass, more preferably at most 50% by mass. Setting the value above the lower limit tends to increase the coloring power and making it possible to support a wide color gamut, and setting the value below the upper limit increases the proportion of components other than the colorant in the colored resin composition and improves patterning properties. There is a tendency to improve.

A dye can be preferably used as the red colorant (a-1). While pigments are aggregates of molecules, dyes exist as single molecules, so they tend to have high brightness and contrast.

Preferred examples of the dye include azo dyes, anthraquinone dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, dipyrromethene dyes, and xanthene dyes. However, xanthene dyes are preferred from the viewpoint of brightness and heat resistance.

Among the xanthene dyes used in the red colorant (a-1), from the viewpoint of heat resistance and contrast, a xanthene compound having a chemical structure represented by the following general formula (1) is preferable.

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
a represents an integer from 2 to 5.
R ⁵ represents an arbitrary substituent, and a plurality of R ⁵ may be different from each other, two or more of which are monovalent groups having at least one selected from the group consisting of -SO ₃ ^- and -COO ^- represents.
M represents a metal atom.
l, m and n each independently represent an integer from 1 to 5, and l=m×n. )

(R ¹ to R ⁴ )
In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
Examples of the alkyl group for R ¹ to R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 12 or less, and more preferably 6 or less. When the value is equal to or higher than the lower limit, heat resistance is improved and a decrease in brightness tends to be suppressed. When the content is below the upper limit, the solubility in the developer improves, and there is a tendency to suppress residues.
The above upper and lower limits can be arbitrarily combined. For example, the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 2 to 6 carbon atoms.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group, and 3-methylbutyl group. Examples include groups. From the viewpoint of ease of synthesis, ethyl group is preferred.

Examples of the substituents that the alkyl group may have include the groups described in the substituent group W1 described below. Examples of the alkyl group having a substituent include a phenethyl group, a 2-ethoxyethyl group, and a 4,4,4-trifluorobutyl group.

Examples of the aromatic ring group for R ¹ to R ⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. There is a tendency for heat resistance to improve by setting it as the above-mentioned lower limit or more. When the content is below the upper limit, the solubility in the developer improves, and there is a tendency to suppress residues.
The above upper and lower limits can be arbitrarily combined. For example, the aromatic hydrocarbon ring group and the aromatic heterocyclic group preferably have 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, even more preferably 4 to 8 carbon atoms, and particularly preferably 6 to 8 carbon atoms.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, each having one free valence; Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, and carbazole rings 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,
Examples include triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
From the viewpoint of heat resistance, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of the substituents that the aromatic ring group may have include the groups described in substituent group W2 described below.

From the viewpoint of heat resistance and ease of synthesis, it is more preferable that all of R ¹ to R ⁴ are ethyl groups.

(a)
a represents an integer from 2 to 5. From the viewpoint of ease of synthesis, a is preferably 2.

( ^R5 )
R ⁵ represents an arbitrary substituent, and a plurality of R ⁵ may be different from each other, two or more of which are monovalent groups having at least one selected from the group consisting of -SO ₃ ^- and -COO ^- represents. From the viewpoint of ease of synthesis and heat resistance, R ⁵ is preferably -SO ₃ ^- .

In addition to the above-mentioned -SO ₃ ^- and -COO ^- , examples of R ⁵ include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent.

Examples of the alkyl group for R ⁵ include linear, branched, or cyclic alkyl groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 3 or less. There is a tendency for heat resistance to improve by setting it as the above-mentioned lower limit or more. When the content is below the upper limit, solvent affinity tends to improve and stability over time tends to improve.
The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1.

Examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylhexyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylethyl group. and 3-methylbutyl group. From the viewpoint of ease of synthesis, a methyl group is preferred.
The alkyl group may be substituted with a group described in substituent group W1 described below.

Examples of the aromatic ring group for R ⁵ include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less. For example, 2 to 12 is preferable, and 6 to 12 is more preferable. There is a tendency for heat resistance to improve by setting it as the above-mentioned lower limit or more. When the content is below the upper limit, solvent affinity tends to improve and stability over time tends to improve.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of aromatic hydrocarbon ring groups include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetracene rings, pyrene rings, benzpyrene rings, chrysene rings, triphenylene rings, each having one free valence; Examples include an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of aromatic heterocyclic groups include furan rings, benzofuran rings, thiophene rings, benzothiophene rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings, indole rings, and carbazole rings 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,
Examples include triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. From the viewpoint of brightness, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of the substituents that the aromatic ring group may have include the groups described in substituent group W2 described below.

(Substituent group W1)
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkenyl group having 2 to 8 carbon atoms; alkoxyl group having 1 to 8 carbon atoms; aromatic carbonization such as phenyl group, mesityl group, tolyl group, naphthyl group, etc. Hydrogen ring group; cyano group; carboxy group; acetyloxy group; carbon number 2~
9 alkylcarbonyloxy group; sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; alkylcarbonyl group having 2 to 9 carbon atoms; phenethyl group; hydroxyethyl group;
Acetylamide group; dialkylaminoethyl group formed by bonding an alkyl group with 1 to 4 carbon atoms; trifluoromethyl group; trialkylsilyl group with 1 to 8 carbon atoms; nitro group;
8 alkylthio group.
Preferably alkoxyl groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, and 2 to 8 carbon atoms.
8 alkylcarboxy group, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom.

(Substituent group W2)
Halogen atoms such as fluorine, chlorine, bromine, and iodine; alkyl groups having 1 to 8 carbon atoms; alkenyl groups having 2 to 8 carbon atoms; hydroxy groups; alkoxyl groups having 1 to 8 carbon atoms:
Aromatic hydrocarbon ring groups such as phenyl group, mesityl group, tolyl group, naphthyl group; cyano group; carboxy group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfonic acid group; sulfamoyl group; number of carbon atoms 2-9 alkylsulfamoyl group; carbonyl group; alkylcarbonyl group having 2-9 carbon atoms; hydroxyethyl group; acetylamide group; carbon number 1
A dialkylaminoethyl group formed by bonding ~4 alkyl groups; a trifluoromethyl group; a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, an alkylthio group having 1 to 8 carbon atoms.
Preferably, an alkyl group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a cyano group,
Acetyloxy group, alkylcarboxy group having 2 to 8 carbon atoms, sulfamoyl group, 2 carbon atoms
-9 alkylsulfamoyl group and a fluorine atom.

(Substituent group W3)
Halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom; alkyl group having 1 to 8 carbon atoms; alkenyl group having 2 to 8 carbon atoms; alkoxyl group having 1 to 8 carbon atoms; phenyl group, mesityl group, tolyl group, aromatic hydrocarbon ring group such as naphthyl group; cyano group; carboxy group; acetyloxy group; alkylcarbonyloxy group having 2 to 9 carbon atoms; sulfamoyl group; alkylsulfamoyl group having 2 to 9 carbon atoms; Alkylcarbonyl group having 2 to 9 carbon atoms; phenethyl group; hydroxyethyl group; acetylamide group; dialkylaminoethyl group formed by bonding an alkyl group having 1 to 4 carbon atoms; trifluoromethyl group; trifluoromethyl group having 1 to 8 carbon atoms; Alkylsilyl group; nitro group; alkylthio group having 1 to 8 carbon atoms.
Preferably alkoxyl groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, and 2 to 8 carbon atoms.
8 alkylcarboxy group, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom.

(M)
M represents a metal atom. M may be any metal as long as it emits electrons and becomes a cation to form an ion pair, and preferable examples thereof include alkali metals and alkaline earth metals. Among these, it is preferable to use alkaline earth metals because they become divalent cations and form aggregates with anions of xanthene dyes, improving heat resistance.

Examples of alkaline earth metals include calcium, strontium, barium, and radium, with calcium being preferred from the viewpoint of ease of synthesis.

(l, m and n)
l, m and n each independently represent an integer from 1 to 5, and l=m×n. From the viewpoint of ease of synthesis, l=2, m=2, and n=1 are preferable.

Specific examples of the xanthene compound having the chemical structure represented by the general formula (1) include the following compounds.

As a method for producing a xanthene compound having a chemical structure represented by general formula (1), a known method can be adopted, for example, a method described in Japanese Patent Application Publication No. 2020-23660 can be adopted. I can do it.

The colorant (A) may contain other colorants in addition to the red colorant (a-1).
Other colorants include pigments and dyes. When used for red pixels, for example, it is preferable to use a red pigment, a yellow pigment, or a red or yellow dye.

As a red pigment, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 4
7, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50
:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 5
7:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 8
1, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101
:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123
, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172
, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185
, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208
, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232
, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247
, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259
, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270
, 271, 272, 273, 274, 275, and 276. Among these, C. I. Pigment Red 48:1, 122, 168, 177, 202, 2
06, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5
, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35
, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53,
55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 86, 87
, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110
, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 1
28, 129, 133, 134, 136, 137, 138, 139, 142, 147, 1
48, 150, 151, 153, 154, 155, 157, 158, 159, 160, 1
61, 162, 163, 164, 165, 166, 167, 168, 169, 170, 1
72, 173, 174, 175, 176, 180, 181, 182, 183, 184, 1
85, 188, 189, 190, 191, 191:1, 192, 193, 194, 195
, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206
, 207, 208, and azobarbituric acid represented by the following formula (i) with nickel:
Examples include compounds in which another compound is inserted into one complex or a tautomer thereof (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

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

Among these, C. I. pigment yellow 83, 11
7, 129, 138, 139, 154, 155, 180, 185, and the nickel azo complex represented by formula (i) are preferred, and C. I. Pigment Yellow 83, 138, 139, 1
80, 185 and the nickel azo complex represented by formula (i) are more preferred.

Examples of red or yellow dyes include azo dyes such as C.I. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Direct Red 28, C. I. Direct Red 83, C.
I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C
．． I. Disperse Orange 5, C. I. Dispersed Red 58, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Examples include Mordant Yellow 5.

Examples of anthraquinone dyes include C.I. I. Examples include Dispersed Red 60 and the like.

Examples of quinoline dyes include C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Examples include Disperse Yellow 64.

Examples of nitro dyes include C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. Examples include Disperse Yellow 42.

As the dipyrromethene dye, for example, JP-A No. 2008-292970, JP-A No. 20
10-84009, JP 2010-84141, JP 2010-85454
No. 2011-158654, 2012-158739, 2012-224852, 2012-224849, 2012-2
Examples include those described in JP-A No. 24847, JP-A No. 2012-224846, and the like.

Examples of xanthene dyes include C.I. I. Acid Red 50, C. I. Acid Red 52, C. I. Acid Red 289, JP 2019-159169, JP 06897685, JP 3387541, JP 2010-32999, JP 4492760, "Overview of synthetic dyes" (written by Hiroshi Horiguchi, Sankyo Publishing) , 1968
Examples include those described on pages 326 to 348).

The average primary particle diameter of the pigment is usually 0.2 μm or less, preferably 0.1 μm or less, and more preferably 0.04 μm or less. For example, solvent salt milling is preferably used to atomize the pigment.

[1-1-2] Red colorant (a-2)
Among the colorants corresponding to the red colorant (a-2), examples of pigments include C.I. I. Pigment Red 264, C. I. Pigment Red 269, C. I. Pigment Red 177 is excluded. In addition, as a dye, C. I. Examples include Acid Red 52 and its derivatives.

The content of the red colorant (a-2) is preferably 1% by mass or more, more preferably 3% by mass or more, particularly preferably 5% by mass or more, based on the total amount of the (A) colorant. Moreover, it is preferably 15% by mass or less, and more preferably 10% by mass or less. When the content is equal to or more than the lower limit value, the coloring power tends to increase and a wide color gamut can be supported, and when it is equal to or less than the upper limit value, the contrast tends to increase.

The content ratio of the colorant (A) is preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably 40% by mass or more based on the total solid content of the colored resin composition. 60 again
It is preferably at most 50% by mass, more preferably at most 50% by mass. Setting the value above the lower limit tends to increase the coloring power and making it possible to support a wide color gamut, and setting the value below the upper limit increases the proportion of components other than the colorant in the colored resin composition and improves patterning properties. There is a tendency to improve.

A dye can be preferably used as the red colorant (a-2). While pigments are aggregates of molecules, dyes exist as single molecules, so they tend to have high brightness and contrast.

Preferred examples of the dye include azo dyes, anthraquinone dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, dipyrromethene dyes, and xanthene dyes. However, xanthene dyes are preferred from the viewpoint of brightness and heat resistance.

Among the xanthene dyes used in the red colorant (a-2), from the viewpoint of heat resistance and contrast, a xanthene compound having the chemical structure represented by the general formula (1) is preferable.

Regarding possible structures and specific examples of the xanthene compound having the chemical structure represented by the general formula (1), those exemplified for the red colorant (a-1) are preferably mentioned.

As a method for producing a xanthene compound having a chemical structure represented by general formula (1), a known method can be adopted, for example, a method described in Japanese Patent Application Publication No. 2020-23660 can be adopted. I can do it.

The colorant (A) may contain other colorants in addition to the red colorant (a-2).
As other colorants, those mentioned above are preferably mentioned.

[1-2] (B) Solvent (B) Solvent dissolves or disperses the colorant, alkali-soluble resin, photoinitiator, photopolymerizable monomer, and other components in the colored resin composition of the present invention, It has the function of adjusting viscosity.
(B) Any solvent may 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;

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

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Etherketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile are mentioned.

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

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

Glycol alkyl ether acetates may be used alone or in combination with other solvents. Particularly preferred solvents used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferred from the viewpoint of solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers are highly polar;
If the amount added is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained later tends to increase, so when using glycol monoalkyl ethers in combination, (B) The proportion of glycol monoalkyl ethers in the solvent is 5% by mass
It is preferably from 30% by weight, more preferably from 5% to 20% by weight.

In another embodiment, a solvent having a boiling point of 150° C. or higher can be used in combination. By using a solvent with a boiling point of 150°C or higher, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult to destroy the mutual relationships among the constituent components in the pigment dispersion due to rapid drying. . When a solvent with a boiling point of 150°C or higher is used in combination, the content of the solvent with a boiling point of 150°C or higher in the solvent (B) is preferably 3% by mass to 50% by mass, and 5% by mass to 40% by mass.
is more preferred, and 5% by mass to 30% by mass is particularly preferred. By setting the above lower limit value or more,
For example, it tends to be easier to avoid colorant components from precipitating and solidifying at the tip of the slit nozzle, causing foreign matter defects, and by setting the value below the above upper limit, the drying rate of the composition slows down, resulting in a vacuum drying process. It tends to be easier to avoid problems such as takt failure and pre-bake pin marks.
The solvent with a boiling point of 150° C. or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, there is no need to separately contain a solvent with a boiling point of 150° C. or higher.
As the solvent having a boiling point of 150° C. or higher, 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, and triacetin.

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

When manufacturing color filters using the inkjet method, the ink emitted from the nozzle is very fine, ranging from several to several tens of pL, so the solvent evaporates and the ink condenses and dries before it lands around the nozzle opening or within the pixel bank. It tends to harden. To avoid this, (B
) It is preferable that the solvent contains a solvent with a high boiling point, and specifically, it is preferable that the solvent contains a solvent with a boiling point of 180° C. or higher. It is more preferable to include a solvent with a boiling point of 200°C or higher, and a boiling point of 22
It is particularly preferable to include a solvent having a temperature of 0° C. or higher. The content of the solvent having a boiling point of 180°C or higher in the solvent (B) is preferably 50% by mass or higher, more preferably 70% by mass or higher, and 9% by mass or higher.
Most preferably, it is 0% by mass or more. By setting it to the above lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.

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

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

Although the content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, the upper limit thereof is as follows:
It is usually 99% by mass or less, preferably 90% by mass or less, more preferably 85% by mass or less. When the amount is below the upper limit, it tends to be easier to form a coating film. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass, considering the viscosity suitable for coating.
It is at least 80% by mass, more preferably at least 80% by mass. The above upper and lower limits can be arbitrarily combined. For example, the content of the solvent in the colored resin composition is preferably 70 to 99% by mass, more preferably 75 to 90% by mass, and even more preferably 80 to 85% by mass.

[1-3] (C) Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing the alkali-soluble resin (C), it is possible to achieve both film curability by photopolymerization and solubility by developer.
(C) Alkali-soluble resins include, for example, Japanese Unexamined Patent Publication No. 7-207211, Japanese Unexamined Patent Publication No. 8-259876, Japanese Unexamined Patent Application No. 10-300922, Japanese Unexamined Patent Application No. 11-140144, Japanese Unexamined Patent Publication No. 11-174224, Japanese Unexamined Patent Publication No. 2
Known polymer compounds described in Japanese Patent Publication No. 000-56118 and Japanese Patent Application Publication No. 2003-233179 can be used. Among them, the following (C-1) to (C-5) are preferable.
The following resins are mentioned.
(C-1): A copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, in which an unsaturated monobasic acid is added to at least a portion of the epoxy groups in the copolymer. An alkali-soluble resin obtained by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction (hereinafter sometimes referred to as "resin (C-1)"). )
(C-2) Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter referred to as “resin”)
C-2). )
(C-3) A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as "resin (C-3)").
(C-4) (meth)acrylic resin (hereinafter sometimes referred to as "resin (C-4)").
)
(C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter referred to as "resin (
C-5). )
Among these, resin (C-1) is particularly preferred.

The resins (C-2) to (C-5) may be dissolved in an alkaline developer and have a solubility to the extent that the intended development process can be carried out, and each of them is disclosed in JP-A-2009-02.
Resins described in the same item in Japanese Patent No. 5813 can be preferably employed.

One of the preferred embodiments of the resin (C-1) is "a copolymer of 5 to 90 mol% of epoxy group-containing (meth)acrylate and 10 to 95 mol% of another radically polymerizable monomer," A resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol% of the epoxy groups possessed by the copolymer, or a resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction. Alkali-soluble resin obtained by

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

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

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

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

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

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

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

Other radically polymerizable monomers other than the mono(meth)acrylate represented by formula (VI) are not particularly limited, but specific examples include styrene, styrene α-,
Vinyl aromatics such as o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; methyl (meth)acrylate, ( Ethyl meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, (
sec-butyl meth)acrylate, tert-butyl (meth)acrylate, (meth)
Pentyl acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, ( cyclopentyl meth)acrylate,
Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate,
Dicyclohexyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Propargyl (meth)acrylate, Phenyl (meth)acrylate, (
Naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, piperonyl (meth)acrylate, salicyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, Tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, 1,1,1-trifluoro(meth)acrylate Ethyl, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-iso-propyl (meth)acrylate, triphenylmethyl (meth)acrylate, (meth)acrylic acid cumyl, (meth)acrylic acid 3-(N,
N-dimethylamino)propyl, (meth)acrylic acid-2-hydroxyethyl, (meth)
(Meth)acrylic acid esters such as 2-hydroxypropyl acrylate; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N
-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-iso-propylamide, (meth)acrylic acid anthracenylamide, etc.
Meth)acrylic acid amide; (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-
Vinyl compounds such as vinylpyrrolidone, vinylpyridine, and vinyl acetate; Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate; N-phenylmaleimide, N-cyclohexylmaleimide, N- Monomaleimides such as laurylmaleimide and N-(4-hydroxyphenyl)maleimide; N
-(Meth)acryloyl phthalimide.

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

A known solution polymerization method can be applied to the copolymerization reaction of the epoxy group-containing (meth)acrylate and other radically polymerizable monomers. The solvent used is not particularly limited as long as it is inert to radical polymerization, and commonly used organic solvents can be used.
Examples of solvents used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, and butyl carbitol acetate; Alkyl ether acetates; Propylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol, butyl carbitol ; Triethylene glycol dialkyl ethers; Propylene glycol dialkyl ethers; Dipropylene glycol dialkyl ethers; Ethers such as 1,4-dioxane and tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Hydrocarbons such as benzene, toluene, xylene, octane, and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha; Methyl lactate, ethyl lactate,
Examples include lactic acid esters such as butyl lactate; dimethylformamide and N-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 usually 30 to 1000 parts by weight, preferably 50 to 800 parts by weight, based on 100 parts by weight of the resulting copolymer. By controlling the amount of solvent used within the above range, it tends to become easier to control the molecular weight of the copolymer.
The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. . Examples of the organic peroxide catalyst include catalysts classified as known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxy esters, and peroxydicarbonates.

Examples of the radical polymerization initiator used in the copolymerization reaction include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, and t-hexyl peroxybenzoate. ,
t-Butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2, 5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3
, 3-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-butylperoxy) 3, 3,5-
Examples include trimethylcyclohexane and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.

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

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

In the present invention, as a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, repeating units 5 to 5 derived from an epoxy group-containing (meth)acrylate are used.
90 mol% and 10 to 95 mol% of repeating units derived from other radically polymerizable monomers; 20 repeating units derived from epoxy group-containing (meth)acrylates.
More preferably, those consisting of ~80 mol% and 80 to 20 mol% of repeating units derived from other radically polymerizable monomers; 30 to 70 mol% of repeating units derived from epoxy group-containing (meth)acrylate and others Particularly preferred are those consisting of 70 to 30 mol% of repeating units derived from radically polymerizable monomers.

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

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

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

Further, as the polybasic acid anhydride to be added to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, a known polybasic acid anhydride can be used.
Examples of polybasic acid anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride,
Dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, etc. Examples include anhydrides of acids having three or more bases. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

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

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

Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group.
As a commercially available product, for example, the product name "Denacol EX-111" manufactured by Nagase ChemteX Co., Ltd.
, "Denacol EX-121", "Denacol EX-141", "Denacol EX-14"
5", "Denacol EX-146", "Denacol EX-171", "Denacol EX-
192''.

The structure of the resin (C-1) is disclosed in, for example, Japanese Unexamined Patent Publication No. 8-297366 and Japanese Unexamined Patent Publication No. 2.
It is described in Publication No. 001-89533.
The weight average molecular weight of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000. By setting it above the above-mentioned lower limit, heat resistance and film strength tend to be good, and by setting it below the above-mentioned upper limit, solubility in a developer tends to become good.
As a guideline for molecular weight distribution, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mw/Mn) of the resin (C-1) is preferably 2.0 to 5.0.

From the viewpoint of coating film curability upon exposure to ultraviolet rays, among (C) alkali-soluble resins, (c1)
Acrylic copolymer resins having ethylenically unsaturated groups in their side chains are preferred.
(c1) The partial structure containing the side chain having an ethylenically unsaturated group in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but the coating film curability upon exposure to ultraviolet rays and alkaline development From the viewpoint of achieving both alkali solubility and alkali solubility, it is preferable to have, for example, a partial structure represented by the following general formula (CI).

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

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

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

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

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by formula (CI), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by formula (CI) is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more,
More preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and preferably 95 mol% or less, more preferably 90 mol% or less, 8
It is more preferably 5 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less, and most preferably 70 mol% or less. By setting it above the above lower limit, there is a tendency for the coating film curability during exposure to ultraviolet rays to improve, and when setting it below the above upper limit, the alkali solubility during alkali development tends to improve. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the partial structure represented by the formula (CI) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 10 to 95 mol%,
It is more preferably 20 to 90 mol%, even more preferably 30 to 85 mol%, even more preferably 40 to 80 mol%, particularly preferably 50 to 75 mol%, and most preferably 65 to 70 mol%.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by formula (CI'), (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain The content ratio of the partial structure represented by formula (CI') contained in is not particularly limited, but 1
It is preferably 0 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and The content is 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. When the value is equal to or more than the lower limit, the coating film curing property during exposure to ultraviolet rays tends to be improved, and when the value is equal to or less than the upper limit, the alkali solubility during alkali development tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, the content of the partial structure represented by formula (CI) contained in (c1) the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferably 10 to 95 mol%, and 20 to 90 mol%. is more preferable, 30 to 85 mol% is even more preferable, and 40 to 8 mol% is more preferable.
0 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 having an ethylenically unsaturated group in the side chain contains a partial structure represented by formula (CI), other partial structures included are not particularly limited, but alkaline dissolution during alkali development From the viewpoint of properties, it is also preferable to have a partial structure represented by the following general formula (CII), for example.

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

( ^R4 )
In formula (CII), R ⁴ represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent.
Examples of the alkyl group for R ⁴ include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more,
It is particularly preferably 8 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. Setting the value above the lower limit tends to improve lipophilicity and improving solubility in solvents, while setting the value below the upper limit tends to improve hydrophilicity and improve alkali solubility. be. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in an alkyl group is 1 to 2.
0 is preferable, 1 to 18 are more preferable, 3 to 16 are even more preferable, 5 to 14 are even more preferable, and 8 to 12 are particularly preferable.

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

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

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

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

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

R ⁴ is an alkyl group that may have a substituent, an aromatic ring group that may have a substituent,
or represents an alkenyl group which may have a substituent, and from the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by formula (CII), (c1) In the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, The content ratio of the partial structure represented by formula (CII) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, and 2
It is particularly preferably at least 0 mol%, preferably at most 70 mol%, more preferably at most 60 mol%, even more preferably at most 50 mol%, and particularly preferably at most 40 mol%. When the content is equal to or more than the lower limit, the alkali solubility tends to improve, and when the content is equal to or less than the upper limit, the storage stability of the colored resin composition tends to improve. The above upper and lower limits can be arbitrarily combined. For example, the content of the partial structure represented by formula (CII) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%. , more preferably 10 to 50 mol%, more preferably 20 to 4
Particularly preferred is 0 mol%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by formula (CIII), (c1) In the acrylic copolymer resin having an ethylenically unsaturated group in the side chain, The content ratio of the partial structure represented by formula (CIII) is not particularly limited, but 1
preferably mol% or more, more preferably 2 mol% or more, even more preferably 5 mol% or more,
It is particularly preferably at least 8 mol%, preferably at most 50 mol%, more preferably at most 40 mol%, even more preferably at most 30 mol%, and particularly preferably at most 20 mol%. Setting the value above the lower limit tends to improve heat resistance and suppressing a decrease in brightness, and setting the value below the upper limit increases the content of other partial structures and tends to improve alkali solubility. . The above upper and lower limits can be arbitrarily combined. For example, the content of the partial structure represented by formula (CIII) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is preferably 1 to 50 mol%, more preferably 2 to 40 mol%. , 5 to 30 mol% is more preferable, and 8 to 20 mol% is particularly preferable.

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

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

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

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

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

The content ratio of the alkali-soluble resin (C) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more in the total solid content of the colored resin composition. % or more is more preferable, 30 mass % or more is even more preferable, and 4
It is particularly preferably at least 0% by mass, preferably at most 80% by mass, more preferably at most 70% by mass, even more preferably at most 60% by mass, and particularly preferably at most 50% by mass. When the amount is equal to or more than the lower limit, the coating film curing property upon exposure to ultraviolet rays tends to be improved, and when it is equal to or less than the upper limit, the developer solubility tends to be improved and residues are suppressed. The above upper and lower limits can be arbitrarily combined. For example, the content of the alkali-soluble resin (C) in the colored resin composition is preferably 5 to 80% by mass in the total solid content of the colored resin composition,
It is more preferably 10 to 80% by weight, even more preferably 20 to 70% by weight, even more preferably 30 to 60% by weight, and particularly preferably 40 to 50% by weight.

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

As the photopolymerization initiator, for example, Japanese Patent Application Publication No. 59-152396, Japanese Patent Application Publication No. 6
Metallocene compounds including titanocene compounds described in each publication No. 1-151197, and N- such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Publication No. 10-39503. aryl-α-amino acids,
Radical activators such as N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone compounds, and oxime ester-based starters described in Japanese Patent Application Publication No. 2000-80068. Examples include agents.

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-
Halomethylated triazine derivatives such as triazine;

2-Trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxa Diazole, 2-trichloromethyl-5-[β-(2'-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3
, 4-oxadiazole and other halomethylated oxadiazole derivatives;
2-(2'-chlorophenyl)-4,5-diphenylimidasole dimer, 2-(2'
-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2
-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-
Imidazole derivatives such as (methoxyphenyl)-4,5-diphenylimidazole dimer and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-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-(
Acetophenone derivatives such as methylthio)phenyl]-2-morpholinopropan-1-one, 1,1,1-trichloromethyl-(p-butylphenyl)ketone;
Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-
Thioxanthone derivatives such as chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, Dicyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3 , 4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-
titanocene derivatives such as 1-yl, dicyclopentajenyl-Ti-2,6-difluoro-3-(pyl-1-yl)-pheny-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)butane-
1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone,
α- such as 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc. Aminoalkylphenone compounds;
1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- yl]-1-(O-acetyloxime) and other oxime ester compounds.

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

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

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

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

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

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

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

Examples of substituents that the carbazolyl group may have include alkyl groups having 1 to 10 carbon atoms such as methyl and ethyl groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy and ethoxy groups; F, Halogen atoms such as Cl, Br, I; Acyl group having 1 to 10 carbon atoms; 1 to 1 carbon atoms
10 alkyl ester group; alkoxycarbonyl group having 1 to 10 carbon atoms; 1 to 10 carbon atoms
halogenated alkyl group; 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; aroyl group which may have a substituent; Examples include a heteroaroyl group which may have a substituent; and a thenoyl group which may have a substituent.

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

The number of carbon atoms in the aroyl group in ^R22a is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. It is. The above upper and lower limits can be arbitrarily combined.
For example, the aroyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 15 carbon atoms, and 7 to 10 carbon atoms.
is more preferred, and 8 to 10 is particularly preferred.
Examples of the aroyl group include benzoyl group and naphthoyl group.
Examples of substituents that the aroyl group may have include 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 to the i-line (365 nm) of the exposure light source. It will be done.

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

The number of carbon atoms in the alkyl group in ^R23a is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and Preferably it is 5 or less. The above upper and lower limits can be arbitrarily combined. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, even more preferably 1 to 10 carbon atoms, even more preferably 1 to 5 carbon atoms, and particularly preferably 2 to 5 carbon atoms.
Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, and cyclohexyl group.
Examples of substituents that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxy group, a phenyl group, a benzyl group, a cyclohexyl group, and a nitro group.
From the viewpoint of ease of synthesis, it is preferable that it is unsubstituted.
From the viewpoint of solubility in solvents and ease of synthesis, R ^23a is more preferably an ethyl group.

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

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

The number of carbon atoms in the heteroaroyl group in ^R24a is not particularly limited, but from the viewpoint of solubility in solvents, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less,
Preferably it is 15 or less, more preferably 10 or less, still more preferably 9 or less. The above upper and lower limits can be arbitrarily combined. For example, the heteroaroyl group preferably has 7 to 20 carbon atoms, more preferably 8 to 15 carbon atoms, even more preferably 9 to 10 carbon atoms, and particularly preferably 9 carbon atoms.
Examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, and a bromonaphthoyl group.
Examples of the 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 preferable that it is unsubstituted.
From the viewpoint of sensitivity, R ^24a is preferably an aroyl group which may have a substituent,
A benzoyl group is more preferred.

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

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

Specific examples of oxime ester compounds include the following compounds.

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

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

Examples of mercapto group-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1
, 2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene and other mercapto group-containing compounds; hexanedithiol, decanedithiol, butane Diol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate)
-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), 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. From the viewpoint of surface smoothness, compounds having multiple mercapto groups are preferred.

As the mercapto group-containing compound having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and as the aliphatic mercapto group-containing compound, trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol Tetrakis (3-Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Trimethylolpropane Tris (3-Mercaptobutyrate), Pentaerythritol Tetrakis (3-Mercaptobutyrate), Pentaerythritol Tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-
Trion is preferred.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, such as trimethylolpropane tris (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptopropionate).
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, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are 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 ratio of the photopolymerization initiator (D) is not particularly limited, but is preferably 0.5% by mass or more, and 0.8% by mass or more in the total solid content of the colored resin composition. is more preferably 1.0% by mass or more, further preferably 1.2% by mass or more, further preferably 10% by mass or less, more preferably 8% by mass or less, further preferably 6% by mass or less, and 4% by mass or less. Particularly preferably less than % by mass. Setting the amount above the lower limit value tends to improve the curability of the coating film, and setting it below the upper limit value tends to improve the brightness by reducing visible light absorption. The above upper and lower limits can be arbitrarily combined. For example, in the colored resin composition, the content ratio of the photopolymerization initiator (D) is preferably 0.5 to 10% by mass, more preferably 0.8 to 8% by mass in the total solid content of the colored resin composition. , more preferably 1.0 to 6% by weight, particularly preferably 1.2 to 4% by weight.

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

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

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

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

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

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

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

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more types may be used in combination. Further, if necessary, a polyfunctional monomer not having an acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. Setting the value above the lower limit tends to improve development and dissolution characteristics, while setting the value below the upper limit allows for better manufacturing and handling, resulting in improved photopolymerization performance, pixel surface smoothness, etc. It tends to improve curing properties. Therefore, when using two or more types of polyfunctional monomers with different acid groups, or when using polyfunctional monomers that do not have acid groups together, the acid groups as a whole of the polyfunctional monomers should be adjusted so that they fall within the above range. is preferred.

In the present invention, a more preferable polyfunctional monomer having an acid group is TO
It is a mixture whose main components are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate succinate commercially available as 1382. This polyfunctional monomer and other polyfunctional monomers can also be used in combination. Furthermore, polyfunctional monomers described in paragraphs 0056 and 0057 of Japanese Patent Application Publication No. 2013-140346 can also be used.

In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of the edges of pixels, it is preferable to use the polymerizable monomer described in Japanese Patent Application Publication No. 2013-195971.
From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, Japanese Patent Application Publication No. 2013-1
It is preferable to use the polymerizable monomers described in Japanese Patent No. 95974.

When the colored resin composition of the present invention contains a photopolymerizable monomer, the content of the photopolymerizable monomer (E) is not particularly limited, but it is usually more than 0% by mass in the total solid content of the colored resin composition. Preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or more. It is not more than 40% by mass, more preferably not more than 40% by mass, particularly preferably not more than 30% by mass. When the amount is equal to or more than the lower limit, the curability of the coating film tends to increase, and when it is equal to or less than the upper limit, a decrease in alkali developability tends to be suppressed. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition (E) contains a photopolymerizable monomer, the content of the photopolymerizable monomer is preferably more than 0% by mass and 70% by mass or less, and 5 to 70% by mass, based on the total solid content of the colored resin composition. More preferably 60% by mass or less, further preferably 10 to 50% by mass, even more preferably 15 to 40% by mass, 2
Particularly preferred is 0 to 30% by weight.

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

[1-6-1] Dispersant, dispersion aid When the colored resin composition of the present invention contains a pigment as the colorant (A), it 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 has excellent dispersion stability over time.
Examples of polymeric dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. Examples include system dispersants.
Examples of polymer dispersants include trade names such as EFKA (registered trademark, manufactured by BASF), D
isperBYK (registered trademark, manufactured by BYK Chemie), DISPARON (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical), Polyflow (manufactured by Kyoeisha Chemical), Dispersants described in JP-A No. 2013-119568 can be mentioned.

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

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

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

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

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

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

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

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

In formula (d1), the cyclic structure formed by bonding R ¹ and R ² to each other may be, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. Specific examples include the following cyclic structure (IV).

These cyclic structures may further have a substituent.

In formula (d1), the divalent linking group X is, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ¹³ - group, -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 a -COO-R ¹⁴ - group. be.

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

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

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

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

In formula (d2), n is 1 from the viewpoint of compatibility and dispersibility with binder components such as solvents.
It is preferably at least 2, more preferably at least 2, preferably at most 10, and more preferably at most 5. The above upper and lower limits can be arbitrarily combined. For example, n is preferably 1 to 10, more preferably 2 to 5.

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

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

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

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

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

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

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 phenylmethylene group.
In ^R8 , examples of the substituent that the alkyl group may have include a halogen atom and an alkoxy group.
Examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, and an alkoxy group.
The chain alkyl group represented by R ⁸ includes both straight chain and branched chain alkyl groups.

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

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

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

Repeating units other than the repeating unit represented by formula (d1) may be contained in the A block. Examples of such repeating units include the above-mentioned repeating units derived from (meth)acrylic acid esters. The content of repeating units other than the repeating unit represented by formula (d1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%.
It is mol%, more preferably 0 mol%.

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

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

The amine value of the block copolymer is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, even more preferably 90 mgKOH/g or more, from the viewpoint of dispersibility and developability. 100 mgKOH/g or more is particularly preferable, 105 mgKOH/g or more is particularly preferable, and 150 mgKOH/g or more is particularly preferable.
/g or less is preferable, and 130mgKOH/g or less is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 30 to 150 mgKOH/g is preferable, and 5
More preferably 0 to 150 mgKOH/g, even more preferably 70 to 150 mgKOH/g, even more preferably 90 to 130 mgKOH/g, and even more preferably 100 to 130 mgKOH/g.
is particularly preferred, and 105 to 130 mgKOH/g is particularly preferred.
The amine value herein refers to the amine value in terms of effective solid content, and is a value expressed by the base amount and the equivalent mass of KOH per 1 g of solid content of the dispersant.

The weight average molecular weight of the block copolymer is preferably 1000 to 30,000. When it is within the above range, the dispersion stability becomes good and there is a tendency that dry foreign matter is less likely to be generated during coating by a slit nozzle method.

Block copolymers can be produced by known methods. For example, it can be produced by living polymerization of monomers into which each of the repeating units described above is introduced.
As the living polymerization method, for example, Japanese Unexamined Patent Publication No. 9-62002, Japanese Unexamined Patent Publication No. 2
Publication No. 002-31713, P. Lutz, P. Masson et al, Polym.
．． Bull. 12, 79 (1984), B. C. Anderson, G. D. Andre
Ws et al, Macromolecules, 14, 1601 (1981), K. H
atada, K. Ute, et al, Polym. J. 17,977 (1985), 1
8, 1037 (1986), Koichi Miguchi, Koichi Hatada, Polymer Processing, 36, 366 (1987
), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Science and Technology, 46, 189 (1989), M. Kuroki
,T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R
．． Hertler et al., Macromolecules, 20, 1473 (198
The known method described in 7) can be employed.

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

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 0.5 parts by mass or more, based on 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, it is 40 parts by mass or less, particularly preferably 30 parts by mass or less. By setting it within the above range, there is a tendency that a colored resin composition with excellent dispersion stability and high brightness can be obtained. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a pigment and a dispersant, the content ratio of the dispersant is 1
0.00 parts by mass, preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass,
More preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, 20 to 3 parts by mass.
Particularly preferred is 0 parts by weight.

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

[1-6-2] Surfactant The colored resin composition of the present invention may contain a surfactant, and examples of the surfactant include anionic, cationic, nonionic, amphoteric surfactants, etc. Although various surfactants can be used, nonionic surfactants are preferred since they are less likely to adversely affect various properties.
When the colored resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01% by mass or more in the total solid content of the colored resin composition.
% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more,
Further, it is usually used in a range of 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, particularly preferably 0.3% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the content of the surfactant is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, and 0.0% by mass based on the total solid content of the colored resin composition.
It is more preferably 5 to 0.5% by weight, particularly preferably 0.1 to 0.3% by weight.

[1-6-3] Adhesion Improver The colored resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. Examples of adhesion improvers include silane coupling agents and titanium coupling agents. Silane coupling agents are preferred.
Examples of the silane coupling agent include KBM-402, KBM-403, KBM-
502, KBM-5103, KBE-9007, X-12-1048, X-12-105
0 (manufactured by Shin-Etsu Silicone Co., Ltd.), Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning Co., Ltd.). One type of silane coupling agent may be used alone, or two types of silane coupling agents may be used alone.
More than one species may be used in combination in any combination and ratio.
The photosensitive resin composition of the present invention may contain an adhesion improver other than the silane coupling agent. Examples include phosphoric acid adhesion improvers and other adhesion improvers.

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

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

When the colored resin composition of the present invention contains an adhesion improver, its content is not particularly limited, but it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.1% by mass or more in the total solid content.
．． More preferably 3% by mass or more, particularly preferably 0.4% by mass or more, preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1.5% by mass or less, and 1% by mass or less. Particularly preferred. When the content is equal to or more than the lower limit, patterning properties tend to be improved and pattern adhesion under high humidity conditions tends to be improved, and when the content is equal to or less than the upper limit, the generation of residue tends to be suppressed. The above upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains an adhesion improver, the content ratio is 0.0% in the total solid content.
It is preferably 1 to 3% by weight, more preferably 0.2 to 2% by weight, even more preferably 0.3 to 1.5% by weight, and particularly preferably 0.4 to 1% by weight.

[2] Preparation of colored resin composition Next, a method for preparing the colored resin composition (hereinafter sometimes referred to as resist) of the present invention will be explained.

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

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

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

When a pigment is not included as a coloring agent, a coloring agent, a solvent, an alkali-soluble resin, a photopolymerization initiator, and, if necessary, components other than those mentioned above can be mixed to obtain a uniform solution.
It is preferable to filter the obtained solution using a filter or the like.

[3] Manufacture of color filter substrate The color filter of the present invention has pixels created using the colored resin composition of the present invention.

[3-1] Transparent substrate (support)
The material for the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly(meth)acrylics. thermosetting resin sheets such as resins,
Alternatively, various types of glass can be mentioned. Among these, glass or heat-resistant resin is preferred from the viewpoint of heat resistance.

The transparent substrate and the substrate provided with the black matrix described below are treated with corona discharge treatment, ozone treatment, and various resins such as silane coupling agents and urethane resins as necessary to improve surface properties such as adhesion. A thin film forming process or the like may also be performed. The thickness of the transparent substrate is usually in the range of 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. In addition, when performing thin film formation processing of various resins, the film thickness is
The thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less. For example, it is 0.01-10 μm, 0.05-5 μm.

[3-2] Black Matrix The color filter of the present invention can be manufactured by providing a black matrix on a transparent substrate and further forming usually red, green, and blue pixel images. The colored resin composition of the present invention is suitable for green or blue pixels (resist pattern) among red, green, and blue pixels.
It is preferable to use it as a forming coating liquid. Green or blue pixels (resist pattern)
On a resin black matrix forming surface formed on a transparent substrate using a forming coating liquid, or
A pixel image is formed on a metal black matrix forming surface formed using a chromium compound or other light-shielding metal material by performing coating, heating drying, image exposure, development, and baking hardening.

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a colored resin composition for black matrix. As the light-shielding metal material, metal chromium, chromium compounds such as chromium oxide and chromium nitride, nickel and tungsten alloys, etc. are used, and a plurality of layers of these may be used.
These metal light-shielding films are generally formed by a sputtering method, and after forming a desired film pattern with a positive photoresist, chromium is treated with ceric ammonium nitrate, perchloric acid, and/or nitric acid. For other materials, a black matrix is formed by removing the positive photoresist with a special remover. 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 or sputtering. Next, after forming a coating film of a colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as a stripe, mosaic, or triangle to form a resist image. Thereafter, this coating film can be subjected to an etching process to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a colored resin composition containing a black colorant is used to form a black matrix. For example, one or more black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. Using a colored resin composition containing a black colorant by mixing, the following red color,
A black matrix can be formed in a similar manner to the method of forming green and blue pixel images.

[3-3] Formation of pixels A colored resin composition of one color among red, green, and blue is applied onto a transparent substrate provided with a black matrix, and after drying, a photomask is placed on top of the coating film. A pixel image is formed by image exposure through a photomask, development, and, if necessary, thermal curing or photocuring. By performing this operation for each of the three colored resin compositions of red, green, and blue, a color filter image can be formed.

The colored resin composition for a color filter can be applied 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. Among these, the die coating method significantly reduces the amount of coating liquid used, has no influence from the mist that adheres when using the spin coating method, and furthermore suppresses the generation of foreign matter. It is preferable from this point of view.

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

[3-4] Drying of the coating film After the colored resin composition is applied to the substrate, the coating film is preferably dried (prebaked) by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The pre-drying conditions include the type of solvent component,
It can be selected as appropriate depending on the performance of the dryer used. The drying temperature and drying time are selected depending on the type of solvent component, the performance of the dryer used, etc., but specifically, the drying temperature is usually 40°C or higher, preferably 50°C or higher, and usually 80°C or higher. below ℃, preferably 70
℃ or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 seconds or more.
It is within a range of 3 minutes or less, preferably 3 minutes or less.

The temperature condition for reheating drying is preferably higher than the preliminary drying temperature. In the present invention,
Specifically, the temperature is in the range of 100°C or higher, preferably 105°C or higher, particularly preferably 110°C or higher, and 200°C or lower, preferably 160°C or lower, particularly preferably 130°C or lower. Setting the amount above the lower limit tends to increase the dissolution rate, while setting it below the upper limit tends to cause the binder resin to decompose, induce thermal polymerization, and cause poor development.

The drying time for reheating drying depends on the heating temperature, but is usually 10 seconds or more, especially 15 seconds or more.
Moreover, it is usually 10 minutes or less, preferably within a range of 5 minutes.

[3-5] Exposure step Image exposure is performed 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. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from decreasing due to oxygen, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the image exposure described above is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating light with a specific wavelength.

[3-6] Development process The color filter according to the present invention has a coating film using the colored resin composition according to the present invention.
After performing image exposure using the above light source, development is performed using an aqueous solution containing a surfactant and an alkaline compound, whereby an image can be formed and manufactured on a substrate.
This aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

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

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

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Organic solvents can be used in combination with aqueous solutions.
There are no particular restrictions on the conditions for development, but the development temperature is usually 10°C or higher, especially 15°C or higher, and even 20°C or higher, and usually 50°C or lower, especially 45°C or lower, and even 40°C or lower. is preferred. The developing method can be any method such as an immersion developing method, a spray developing method, a brush developing method, an ultrasonic developing method, or the like.

[3-7] Thermosetting treatment After development, the color filter is subjected to a thermosetting treatment. The heat curing treatment conditions at this time are usually 100°C or higher, preferably 150°C or higher, and usually 280°C or lower, preferably 280°C or higher.
The temperature is selected within the range of 50°C or less, and the time is selected within the range of 5 minutes or more and 60 minutes or less. Through these series of steps, the formation of a single color patterning image is completed. Repeat this process sequentially,
Pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the above order.

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

[4] Image display device (panel)
The 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 a liquid crystal display device according to the present invention will be described. The liquid crystal display device according to the present invention is usually produced by forming an alignment film on the color filter of the present invention, scattering spacers on the alignment film, and then bonding it to a counter substrate to form a liquid crystal cell. Complete the process by injecting liquid crystal into the cell and connecting it to the counter electrode. The alignment film is preferably a resin film such as polyimide. Gravure printing and/or flexographic printing are usually used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After the alignment film is hardened by thermal baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface condition that allows adjustment of the tilt of the liquid crystal.

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

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

Heating and holding during reduced pressure is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in liquid crystal. A liquid crystal display device (panel) is completed by curing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected and sealing it with a UV curing resin.
The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, etc.
Nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, and the like are known as thermotropic liquid crystals, but any of them may be used.

[4-2] Organic EL Display Device When creating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. A multicolor organic EL device is manufactured by stacking an organic light emitter 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40 interposed therebetween.

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

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

<Xanthene compound A>
A xanthene compound A having the following chemical structure, which was synthesized based on Example 2 of JP-A-2020-23660, was used. When the compound was dissolved in water at a concentration of 10 ppm and the absorbance spectrum was measured with a measurement cell length of 1 cm using a spectrophotometer U-3310 manufactured by Hitachi, Ltd., the wavelength of the absorption peak on the longest wavelength side was 565 nm. The absorbance at this wavelength was 1.7.

C. I. Pigment Red 269 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 10 ppm, and the absorbance spectrum was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. with a measurement cell length of 1 cm.The wavelength of the absorption peak on the longest wavelength side is 5
At 81 nm, the absorbance at that wavelength was 0.4.

C. I. Pigment Red 264 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 10 ppm, and the absorbance spectrum was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. with a measurement cell length of 1 cm.The wavelength of the absorption peak on the longest wavelength side is 5
At 65 nm, the absorbance at that wavelength was 0.2.

C. I. Pigment Red 177 was dissolved in propylene glycol monomethyl ether acetate at a concentration of 10 ppm, and the absorbance spectrum was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. with a measurement cell length of 1 cm.The wavelength of the absorption peak on the longest wavelength side is 5
At 65 nm, the absorbance at that wavelength was 0.2.

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

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

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

Meanwhile, in the monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 69 parts by mass of methacrylic acid, and monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd. ) 40 parts by mass, t-butylperoxy-2
- 5.2 parts by mass of ethylhexanoate 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 agent tank, and a reaction tank was charged. temperature is 9
After the temperature stabilized at 0°C, dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization.
Each dropwise addition took 135 minutes while maintaining the temperature at 90°C, and 60 minutes after the completion of the dropwise addition, the temperature was started to rise to 110°C.

After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel, and the mixture was reacted at 110°C for 9 hours.
The mixture was cooled to room temperature and the weight average molecular weight (Mw) of the mixture measured by GPC in terms of polystyrene was 19.
As a result, an alkali-soluble resin A having an acid value of 198 mg KOH/g and a double bond equivalent of 550 g/mol was obtained.

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

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

After maintaining the temperature at 110° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were placed in a reaction tank, and the mixture was heated at 110°C. The mixture was allowed to react for 9 hours.
The weight average molecular weight Mw in terms of polystyrene measured by GPC after cooling to room temperature is 90.
00, an alkali-soluble resin B having an acid value of 101 mgKOH/g and a double bond equivalent of 550 g/mol was obtained.

<Preparation of red colorant dispersion A>
As shown in Table 1, 2.6 parts by mass of xanthene compound A, C. I. 10.5 parts by mass of Pigment Red 177, 3.3 parts by mass of dispersant A in terms of solid content, alkali-soluble resin B
5.2 parts by mass in terms of solid content, 72.9 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant A), 8.1 parts by mass of propylene glycol monomethyl ether, diameter 0.5 mm. A stainless steel container was filled with 225 parts by mass of zirconia beads, and a dispersion treatment was performed for 6 hours using a paint shaker. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare a red colorant dispersion liquid A.

<Preparation of red colorant dispersion B>
As shown in Table 1, C. I. 14.3 parts by mass of Pigment Red 269, 4.0 parts by mass of dispersant A in terms of solid content, 4.4 parts by mass of alkali-soluble resin B in terms of solid content, and 68.9 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 B), 8.5 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container, and paint was added. Dispersion treatment was performed for 6 hours using a shaker. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare a red colorant dispersion B.

<Preparation of red colorant dispersion C>
As shown in Table 1, C. I. 14.0 parts by mass of Pigment Red 264, 4.0 parts by mass of dispersant A in terms of solid content, 4.0 parts by mass of alkali-soluble resin B in terms of solid content, and 62.0 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 B), 16.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were filled into a stainless steel container, and paint was added. Dispersion treatment was performed for 6 hours using a shaker. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare a red colorant dispersion C.

<Preparation of red colorant dispersion D>
As shown in Table 1, C. I. 15.0 parts by mass of Pigment Red 177, 2.0 parts by mass of dispersant A in terms of solid content, 4.0 parts by mass of alkali-soluble resin B in terms of solid content, and 79.0 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 B) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container, and dispersed in a paint shaker for 6 hours. After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare a red colorant dispersion D.

<Preparation of yellow colorant dispersion A>
As shown in Table 1, C. I. 13.8 parts by mass of Pigment Yellow 139, dispersant A
3.9 parts by mass in terms of solid content, 4.3 parts by mass in terms of solid content of alkali-soluble resin B, and 70.3 parts by mass of propylene glycol monomethyl ether acetate as a solvent (dispersant A
7.8 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 in a paint shaker for 6 hours. processed. After the dispersion was completed, the beads and the dispersion liquid were separated using a filter to prepare a yellow colorant dispersion liquid A.

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

<Photopolymerization initiator A>
Oxime ester compound with the following chemical structure

<Antioxidant A>
Irganox 1010: Hindered phenolic antioxidant (manufactured by BASF)

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

<Preparation of colored resin composition>
Colored resin compositions 1 to 4 were prepared by mixing the components listed in Table 2 at the solid content ratios listed.
In addition, in colored resin compositions 1 to 4, propylene glycol monomethyl ether acetate (PGMEA) was added so that the total solid content of the colored resin composition was 15% by mass.
and propylene glycol monomethyl ether (PGME). The mixing ratio (mass ratio) of PGMEA/PGME in the obtained colored resin composition was 90/10.

<Measurement of absorption wavelength>
The above colored resin composition was applied by spin coating onto a 50 mm square, 0.5 mm thick glass substrate (manufactured by AGC, AN100) so that the film thickness after thermosetting was 2 μm, and dried under reduced pressure. After that, it was prebaked on a hot plate at 110°C for 70 seconds. Then 2k
The entire surface was exposed using a W high-pressure mercury lamp at an exposure amount of 40 mJ/cm ² and an illuminance of 32 mW/cm ² . Thereafter, baking was performed at 230° C. for 20 minutes in a clean oven to produce a colored substrate.

Using the obtained colored substrate, the transmission spectrum was measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd. After converting the transmission spectrum to an absorption spectrum, the wavelength of the absorption peak at a wavelength of 560 nm or more was measured, and it was 566 nm for colored resin composition 1, 568 nm for colored resin composition 2, and 560 nm for colored resin composition 3. In composition 4, 566n
It was m. Note that the xanthene compounds A and C. I. The absorption peaks on the longest wavelength side of Pigment Red 177 overlap, but C. I. Compared to Colored Resin Composition 4 containing Pigment Red 177 alone, Colored Resin Composition 1 contained 566n
Since the absorption peak of m has increased significantly, it can be determined that the peak is derived from xanthene compound A.

<Measurement of contrast>
The above colored resin composition was applied onto a 50 mm square, 0.5 mm thick glass substrate (manufactured by AGC, AN100) using a spin coating method, dried under reduced pressure, and then coated on a hot plate for 110 mL.
Prebaked at ℃ for 70 seconds. Next, the entire surface was exposed using a 2 kW high-pressure mercury lamp at an exposure amount of 40 mJ/cm ² and an illuminance of 32 mW/cm ² . Then, in a clean oven 2
Baking was performed at 30° C. for 20 minutes to create a colored substrate.

Using the obtained colored substrate, the contrast at a chromaticity of sx=0.686 using a C light source was measured using a contrast meter (CT-1) manufactured by Tsubosaka Electric Co., Ltd. Table 3 shows the measured contrast.

<Evaluation of pattern formation>
The above-mentioned colored resin composition was applied by spin coating onto a glass substrate (manufactured by AGC, AN100) having a size of 50 mm square and a thickness of 0.5 mm. At this time, the chromaticity sx after heat curing treatment is 0.686
The rotation speed was adjusted so that
Each coating film was prebaked at 110° C. for 90 seconds. Next, a 2kW high-pressure mercury lamp was used to
Exposure processing was performed through an exposure mask at an exposure dose of 0 mJ/cm ² and an illuminance of 32 mW/cm ² . Thereafter, using a 0.04% by mass potassium hydroxide aqueous solution, 120%
A second development process was performed. Next, spray water washing treatment was performed for 10 seconds at a water pressure of 1 kg/cm ² . The resulting patterned substrate was observed using an optical microscope to see if a pattern was formed. If a pattern is formed, it is marked ○, and if no pattern is formed, it is marked ×, as shown in Table 3.

As is clear from Table 3, in Example 1, red colorant (a-1) and red colorant (a-2
) By using xanthene compound A as a colorant corresponding to (A), the ratio of red colorant (a-1) and red colorant (a-2) in the colorant was less than 15%, and the contrast value was good. This is because xanthene compound A has a large absorption of light with a wavelength of 560 nm or more, and the desired color (chromaticity coordinates x, y in the XYZ color system is 0.686
, 0.311). Red colorant (a-1) used in Comparative Examples 1 and 2
A coloring agent that does not fall under the red coloring agent (a-2) has relatively low absorption of light with a wavelength of 560 nm or more, and in order to reproduce the desired color, the red coloring agent (A) in the coloring agent ( a-2)
The proportion of colorants applicable to this has increased. This is C.I., which is preferably used as a general-purpose red colorant because of its good contrast. I. Pigment Red 177 and C. I
．． This means that Pigment Red 254 cannot be added or the amount added must be reduced, and therefore Comparative Examples 1 and 2 had low contrast. In Comparative Example 3, C.I., a general-purpose red colorant, was used as the red colorant. I. Since only Pigment Red 177 was used, the contrast was good. However, C. I. Pigment Red 177 is a red colorant (a-1
), absorption of light with a wavelength of 560 nm or more is lower than that of colorants that fall under 560 nm or more, so the amount of colorant added is large in order to reproduce the desired color, and the ratio of materials such as alkali-soluble resins required for pattern formation is reduced. Because the amount decreased, a pattern could not be formed.

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

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

Claims (18)

(A) colorant, (B) solvent, (C) alkali-soluble resin, (D) photoinitiator, and (
E) A colored resin composition containing a photopolymerizable monomer,
When the colorant (A) is measured using water or propylene glycol monomethyl ether acetate as a solvent at a concentration of 10 ppm and a measurement cell length of 1 cm, the absorbance is 1.
A red colorant (a
-1),
A colored resin composition, wherein the content of the colorant (A) is 30% by mass or more based on the total solid content of the colored resin composition. The colored resin composition according to claim 1, wherein the content ratio of the colorant (A) is 50% by mass or less based on the total solid content of the colored resin composition. The colored resin composition according to claim 1, wherein the content of the red colorant (a-1) is 10% by mass or less based on the total amount of the (A) colorant. The colored resin composition according to any one of claims 1 to 3, wherein the red colorant (a-1) is a dye. The colored resin composition according to claim 4, wherein the red colorant (a-1) is a xanthene dye. The colored resin composition according to any one of claims 1 to 3, wherein the red colorant (a-1) is a xanthene compound having a chemical structure represented by the following general formula (1).

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
a represents an integer from 2 to 5.
R ⁵ represents an arbitrary substituent, and a plurality of R ⁵ may be different from each other, two or more of which are monovalent groups having at least one selected from the group consisting of -SO ₂ ^- and -COO ^- represents.
M represents a metal atom.
l, m and n each independently represent an integer from 1 to 5, and l=m×n. ) The colored resin composition according to claim 6, wherein M in the general formula (1) is an alkaline earth metal atom. having a pixel created using the colored resin composition according to any one of claims 1 to 3,
color filter. An image display device comprising the color filter according to claim 8. (A) colorant, (B) solvent, (C) alkali-soluble resin, (D) photoinitiator, and (
E) A colored resin composition containing a photopolymerizable monomer,
A red colorant in which the colorant (A) exhibits an absorption peak at a wavelength of 560 nm or more when measured on a 2 μm thick coating obtained by coating a colored resin composition on a substrate and baking it at 230° C. for 20 minutes. Contains a colorant (a-2) (excluding C.I. Pigment Red 177),
The content ratio of the red colorant (a-2) is 15% by mass or less based on the total amount of the colorant (A),
A colored resin composition, wherein the content of the colorant (A) is 30% by mass or more based on the total solid content of the colored resin composition. The colored resin composition according to claim 10, wherein the content ratio of the colorant (A) is 50% by mass or less based on the total solid content of the colored resin composition. The colored resin composition according to claim 10, wherein the content of the red colorant (a-2) is 10% by mass or less based on the total amount of the (A) colorant. The colored resin composition according to any one of claims 10 to 12, wherein the red colorant (a-2) is a dye. The colored resin composition according to claim 13, wherein the red colorant (a-2) is a xanthene dye. The colored resin composition according to any one of claims 10 to 12, wherein the red colorant (a-2) is a xanthene compound having a chemical structure represented by the following general formula (1).

(In formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
a represents an integer from 2 to 5.
R ⁵ represents an arbitrary substituent, and a plurality of R ⁵ may be different from each other, two or more of which are monovalent groups having at least one selected from the group consisting of -SO ₂ ^- and -COO ^- represents.
M represents a metal atom.
l, m and n each independently represent an integer from 1 to 5, and l=m×n. ) The colored resin composition according to claim 15, wherein M in the general formula (1) is an alkaline earth metal atom. A color filter having pixels made using the colored resin composition according to any one of claims 10 to 12. An image display device comprising the color filter according to claim 17.