JP7779261B2 - Colored resin composition, color filter, and image display device - Google Patents

Description

The present invention relates to a colored resin composition, a color filter, and an image display device.
This application claims priority based on Japanese Patent Application No. 2020-139037, filed on August 20, 2020, the contents of which are incorporated herein by reference.

Conventional methods for manufacturing color filters used in liquid crystal displays and other devices include pigment dispersion, dyeing, electrodeposition, and printing. Among these, the pigment dispersion method is the most widely used, as it offers superior average properties in terms of spectral characteristics, durability, pattern shape, and precision.

In recent years, there has been a demand for color filters with higher brightness, higher contrast, and a wider color gamut. Pigments are generally used as the coloring materials that determine the color of color filters, due to their heat resistance and light resistance. However, pigments are no longer able to meet market demands, particularly for high brightness, and there has been active research into using dyes as coloring materials instead of pigments.

For example, the use of phthalocyanine dyes for green pixel applications has been considered (see, for example, Patent Document 1), and the use of xanthene dyes for blue pixel applications has been considered (see, for example, Patent Document 2).

On the other hand, Patent Document 3 describes that a curable composition containing a specific photopolymerization initiator can achieve both sensitivity, transparency, and brightness.

Japanese Patent Application Publication No. 2019-113732 International Publication No. 2018/052022 Japanese Patent Application Publication No. 2017-179211

As a result of investigations by the present inventors, it was found that in colored resin compositions containing dyes such as those described in Patent Documents 1 and 2, sensitivity varies greatly depending on the temperature during pre-baking (a drying process of the coating film carried out before the exposure process), and pattern size varies greatly particularly in the low temperature range. This has revealed the problem that high-definition color filters, such as 4K8K, which require precise line width adjustment, cannot be stably manufactured.
Furthermore, Patent Document 3 does not evaluate compositions containing dyes, and it is unclear what properties a composition containing a dye would exhibit.

Therefore, the present invention aims to provide a colored resin composition that has little effect on sensitivity due to changes in pre-baking temperature.

As a result of intensive research, the present inventors have found that the above-mentioned problems can be solved by using a specific photopolymerization initiator in a colored resin composition containing a specific dye, and have arrived at the present invention.
That is, the present invention has the following configurations [1] to [8].

[1] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator,
The colorant (A) contains a phthalocyanine dye having a chemical structure represented by the following general formula (1):
The colored resin composition, wherein the (D) photopolymerization initiator contains a photopolymerization initiator (d1) represented by the following general formula (I):

(In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).)

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

(In formula (I), R ^d1 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents an aromatic ring group which may have a substituent.

[2] The colored resin composition according to [1], wherein, in the formula (1), six or more of A ¹ to A ¹⁶ represent fluorine atoms.
[3] A colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator,
The colorant (A) contains a xanthene dye having a chemical structure represented by the following general formula (10):
The colored resin composition, wherein the (D) photopolymerization initiator contains a photopolymerization initiator (d1) represented by the following general formula (I):

In formula (10), R ^a1 to R ^a4 each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^a5 represents —SO ³⁻ or —COO ^— .
n represents an integer of 1 to 5.

(In formula (I), R ^d1 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents an aromatic ring group which may have a substituent.

[4] The colored resin composition according to any one of [1] to [3], wherein in the photopolymerization initiator (d1), R ^d3 is a benzene ring having one free valence and which may have a substituent.
[5] The colored resin composition according to any one of [1] to [4], wherein the content of the colorant (A) is 15 mass% or more of the total solid content.
[6] The colored resin composition according to any one of [1] to [5], wherein the content of the photopolymerization initiator (d1) is 1.0 mass% or more based on the total solid content.
[7] A color filter having pixels formed using the colored resin composition according to any one of [1] to [6].
[8] An image display device having the color filter according to [7].

According to the present invention, a colored resin composition can be provided that has little effect on sensitivity due to changes in pre-baking temperature.

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

In the present invention, the term "weight average molecular weight" refers to the weight average molecular weight (Mw) calculated in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, the term "total solid content" refers to all components in the colored resin composition other than the solvent. Even if a component other than the solvent is liquid at room temperature, that component is not included in the solvent but is included in the total solid content.
In the present invention, unless otherwise specified, the "amine value" refers to the amine value calculated as the effective solid content, and means a value expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content of the dispersant.
In the present invention, "C.I." means Color Index.

[1] Colored Resin Composition Each of the components of the colored resin composition of the present invention will be described below.
The colored resin composition of the first aspect according to the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) colorant contains a phthalocyanine dye having a chemical structure represented by the general formula (1) described below, and the (D) photopolymerization initiator contains a photopolymerization initiator (d1) described below. The colored resin composition of this aspect may further contain other additives and the like in addition to the above components, if necessary.

A colored resin composition according to a second aspect of the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator, wherein the (A) colorant contains a xanthene dye having a chemical structure represented by general formula (10) described below, and the (D) photopolymerization initiator contains photopolymerization initiator (d1) described below. The colored resin composition according to this aspect may further contain additives other than the above components, if necessary.

[1-1] (A) Colorant The colored resin composition of the present invention contains (A) a colorant. The colorant is a component that colors the colored resin composition. By including (A) the colorant, it is possible to obtain the desired light absorption properties.

The colorant (A) in the colored resin composition of the present invention includes a dye. By including a dye, the transmittance is improved, resulting in a colored resin composition with high brightness.
The dye in the present invention refers to a coloring matter compound that is soluble in a specific organic solvent. Examples of the specific organic solvent include the organic solvents exemplified in the solvent section described below, and among these, propylene glycol monomethyl ether acetate is preferred.

In the colored resin composition of the first aspect of the present invention, the colorant (A) contains a phthalocyanine dye having a chemical structure represented by the following general formula (1) (hereinafter, sometimes referred to as "phthalocyanine dye (1)").

In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2):

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

(A ¹ to A ¹⁶ )
In the formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2):

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

Examples of the halogen atom in A ¹ to A ¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom. From the viewpoint of increasing brightness, a fluorine atom is preferred.
Of A ¹ to A ¹⁶ , preferably 6 or more are fluorine atoms, more preferably 7 or more, and even more preferably 8 or more, and preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. By making the number equal to or greater than the lower limit, the stability of the phthalocyanine compound (1) tends to be improved. By making the number equal to or less than the upper limit, the affinity with the dispersant and solvent in the colored resin composition tends to be improved.
The above upper and lower limits can be combined in any desired manner. For example, among A ¹ to A ¹⁶ , 6 to 15 are preferably fluorine atoms, more preferably 7 to 12, and even more preferably 8 to 10.

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

(Substituents that the benzene ring may have)
The benzene ring in formula (2) may have any substituent. Acceptable substituents are not particularly limited, but examples thereof include a halogen atom, an alkyl group, an alkoxy group (-OR ^A group ( ^RA represents an alkyl group)), an alkoxycarbonyl group (-COOR ^A group ( ^RA represents an alkyl group)), an aryl group, an aryloxy group (-OR ^B group ( ^RB represents an aryl group)), and an aryloxycarbonyl group (-COOR ^B group ( ^RB represents an aryl group)). Among these, an alkoxycarbonyl group is preferred from the viewpoints of development solubility and brightness.

The alkyl group contained in these groups may be linear, branched, or cyclic, but is preferably linear from the viewpoint of affinity with organic solvents.
The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less. By making the number equal to or greater than the lower limit, aggregation tends to be suppressed, and foreign matter tends to be suppressed. By making the number equal to or less than the upper limit, solvent affinity tends to be improved, and stability over time tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 2 to 4 carbon atoms.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. From the viewpoint of suppressing aggregation, a methyl group or an ethyl group is preferred, and an ethyl group is more preferred.

The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The number of carbon atoms in the aryl group is not particularly limited, but is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By making the number equal to or greater than the lower limit, aggregation due to steric repulsion tends to be suppressed. By making the number equal to or less than the upper limit, solvent affinity tends to be improved, and stability over time tends to be improved.
The above upper and lower limits can be arbitrarily combined with the number of carbon atoms in the aryl group. For example, 4 to 12 is preferable, 4 to 10 is more preferable, 4 to 8 is even more preferable, and 6 to 8 is particularly preferable.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole ring, a 1,3-thiazole ring, an isothiazole ring, an imidazole ring, a pyrazole ring, a furazan ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,3,5-triazine ring, and a benzofuran ring, each of which has one free valence. , 2-benzofuran ring, benzothiophene ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolizine ring, benzimidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline ring, phthalazine ring, 1,8-naphthyridine ring, purine ring, and pteridine ring.

When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited. However, from the viewpoints of improving heat resistance by π-π stacking between dye molecules and suppressing a decrease in luminance due to decomposition of the dye, it is preferable that the number of substitutions is one per benzene ring.
When the benzene ring in formula (2) has an optional substituent, the substitution position may be the o-position, the m-position, or the p-position, but the p-position is preferred from the viewpoint of enabling stacking to form a close-packed structure.

At least one of A ¹ to A ¹⁶ represents a group represented by the general formula (2). From the viewpoint of solubility in organic solvents and brightness, it is preferable that at least one of A ¹ to A ⁴ is a group represented by the general formula (2), at least one of A ⁵ to A ⁸ is a group represented by the general formula (2), at least one of A ⁹ to A ¹² is a group represented by the general formula (2), and at least one of A ¹³ to A ¹⁶ is a group represented by the general formula (2), and it is more preferable that at least two of A ¹ to A ⁴ are groups represented by the general formula (2), at least two of A ⁵ to A ⁸ are groups represented by the general formula (2), at least two of A ⁹ to A ¹² are groups represented by the general formula (2), and at least two of A ¹³ to A ¹⁶ are groups represented by the general formula (2).
In particular, from the viewpoint of suppressing a decrease in brightness through efficient stacking, it is particularly preferable that ^A2 , ^A3 , ^A6 , ^A7 , ^A10 , ^A11 , ^A14 , and ^A15 are groups represented by the general formula (2) and ^A1 , ^A4 , ^A5 , ^A8 , ^A9 , A12, ^{A13 ,} and ^A16 are halogen atoms.

Specific examples of phthalocyanine dyes (1) include the following:

Phthalocyanine dye (1) can be produced by known methods, such as the method described in Japanese Patent Application Laid-Open No. 05-345861.

In the second aspect of the colored resin composition according to the present invention, the colorant (A) comprises a xanthene dye having a chemical structure represented by the following general formula (10) (hereinafter, sometimes referred to as "xanthene dye (10)").

In formula (10), R ^a1 to R ^a4 each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^a5 represents —SO ³⁻ or —COO ^— .
n represents an integer of 1 or more and 5 or less.

(R ^a1 to R ^a4 )
In the formula (10), R ^a1 to R ^a4 each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group for R ^a1 to R ^a4 may be a linear, branched, or cyclic alkyl group. The number of carbon atoms therein is usually 1 or more, preferably 2 or more, and is preferably 12 or less, more preferably 6 or less. By making the number of carbon atoms equal to or greater than the lower limit, heat resistance tends to be improved and a decrease in brightness tends to be suppressed. By making the number of carbon atoms equal to or less than the upper limit, development solubility tends to be improved.
The above upper and lower limits can be combined in any combination. 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 alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and 3-methylbutyl. From the perspective of ease of synthesis, ethyl, n-propyl, and n-butyl groups are preferred, with n-butyl being more preferred.

Examples of the substituents that the alkyl group may have include the groups described in Substituent Group W1 below. Examples of substituted alkyl groups include a phenethyl group, a 2-ethoxyethyl group, a 4,4,4-trifluorobutyl group, an anilyl group, a vanillyl group, and an N-acetamidophenylbutyl group.

The aromatic ring group in R ^a1 to R ^a4 includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By making the number of carbon atoms equal to or greater than the lower limit, heat resistance tends to be improved and a decrease in brightness tends to be suppressed. By making the number of carbon atoms equal to or less than the upper limit, development solubility tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the number of carbon atoms in the aromatic hydrocarbon ring group and aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, even more preferably 4 to 8, and particularly preferably 6 to 8.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence.
From the viewpoints of heat resistance and ease of synthesis, a benzene ring or naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

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

From the viewpoint of heat resistance, it is preferable that R ^a1 and R ^a2 each independently represent an aromatic ring group which may have a substituent, more preferably a phenyl group substituted with an alkyl group, and even more preferably a phenyl group substituted with an alkyl group at both of the two ortho positions.
From the viewpoint of solubility in a developer, it is preferred that R ^a3 and R ^a4 each independently represent an alkyl group which may have a substituent.

(R ^a5 )
In the formula (10), R ^a5 represents —SO ³⁻ or —COO ^— . From the viewpoint of brightness, —SO ³⁻ is preferred. When a plurality of R ^a5 are present, each R ^a5 may be the same or different.

In formula (10), n represents an integer of 1 or more and 5 or less. By making n equal to or greater than the lower limit, solvent affinity tends to increase and developer solubility tends to improve. By making n equal to or less than the upper limit, aggregation between dyes tends to be suppressed, and the stability over time of the colored resin composition tends to improve. For example, n is preferably an integer of 1 or more and 3 or less.

When n in formula (10) is an integer of 2 or greater, the xanthene dye (10) preferably forms a salt. The cation is preferably an alkali metal or alkaline earth metal, more preferably an alkaline earth metal, and particularly preferably calcium.

Among the xanthene dyes represented by the formula (10), the xanthene dyes represented by the following general formula (11) are preferred from the standpoints of brightness and contrast.

In formula (11), R ¹ and R ² each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
^R3 and ^R4 each independently represent a divalent hydrocarbon group which may have a substituent.
^R5 and ^R6 each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ⁷ represents —SO ³⁻ or —COO ^— .
However, the —CH ₂ — contained in the alkyl group, the aromatic ring group, and the hydrocarbon group may be substituted with at least one selected from the group consisting of —O—, —CO—, —COO—, —CONH—, —CONR ⁸ —, —NH—, —NR ⁸ —, —SO ₂ —, —SO ₂ NH—, —SO ₂ NR ⁸ —, and —S—. R ⁸ represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

( ^R1 , ^R2 )
In the formula (11), R ¹ and R ² each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group in ^R1 and ^R2 may be a linear, branched, or cyclic alkyl group. The number of carbon atoms is usually 1 or more, preferably 2 or more, and preferably 12 or less, more preferably 6 or less. By making the number of carbon atoms equal to or greater than the lower limit, heat resistance tends to be improved and brightness reduction tends to be suppressed. By making the number of carbon atoms equal to or less than the upper limit, solubility in a developer tends to be improved and residues tend to be suppressed.
The above upper and lower limits can be combined in any combination. 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 alkyl groups include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tert-butyl, cyclohexyl, cyclohexylmethyl, cyclohexylethyl, and 3-methylbutyl. From the perspective of ease of synthesis, the ethyl group is preferred.

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

The aromatic ring group in ^R1 and ^R2 includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By making the number of carbon atoms equal to or greater than the lower limit, heat resistance tends to be improved. By making the number of carbon atoms equal to or less than the upper limit, solubility in a developer tends to be improved and residues tend to be suppressed.
The above upper and lower limits can be combined in any combination. For example, the aromatic hydrocarbon ring group and 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 the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence.
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 substituents that the aromatic ring group may have include groups described in the substituent group W2 described below.

From the viewpoint of heat resistance, it is preferable that ^R1 and ^R2 each independently represent an aromatic ring having one free valence and which may have a substituent, more preferably a benzene ring having one free valence and substituted with an alkyl group, and even more preferably a benzene ring having one free valence and substituted with alkyl groups at both of the two ortho-positions.

( ^R3 , ^R4 )
In the formula (11), R ³ and R ⁴ each independently represent a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group may be linear, branched, cyclic, or a combination thereof, such as an alkylene group, an arylene group, or a group in which an alkylene group and an arylene group are linked together.

The number of carbon atoms in the divalent hydrocarbon group is usually 1 or more, preferably 3 or more, more preferably 6 or more, even more preferably 8 or more, and is preferably 20 or less, more preferably 16 or less, even more preferably 14 or less, even more preferably 12 or less, and particularly preferably 11 or less. By making the carbon number equal to or greater than the lower limit, heat resistance tends to be improved. By making the carbon number equal to or less than the upper limit, solubility in a developer tends to be improved and residues tend to be suppressed.
The above upper and lower limits can be combined in any combination. For example, the divalent hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, even more preferably 1 to 14 carbon atoms, even more preferably 3 to 12 carbon atoms, particularly preferably 6 to 11 carbon atoms, and particularly preferably 8 to 11 carbon atoms.

Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, a cyclopentylene group, an n-hexylene group, a cyclohexylene group, and an n-heptylene group. From the viewpoints of heat resistance and solubility, an n-butylene group is preferred.
Examples of the arylene group include o-, m-, or p-phenylene, naphthylene, fluorene, indolene, anthracene, furan, and thiophene groups. From the viewpoint of ease of synthesis, a phenylene group is preferred.
Examples of the group formed by linking an alkylene group and an arylene group include a combination of the above alkylene group and the above phenylene group. From the viewpoints of heat resistance and brightness, a combination of a butylene group and a p-phenylene group is preferred.

Examples of substituents that the divalent hydrocarbon group may have include groups described in the substituent group W3 described below.

From the viewpoint of heat resistance and brightness, it is preferable that ^R3 and ^R4 each independently represent a group in which an optionally substituted alkylene group and an optionally substituted arylene group are linked together, and it is more preferable that R3 and R4 represent a combination of a butylene group and a p-phenylene group.

( ^R5 , ^R6 )
In the formula (11), R ⁵ and R ⁶ each independently represent an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group for ^R5 and ^R6 may be a linear, branched, or cyclic alkyl group. The number of carbon atoms is usually 1 or more, preferably 12 or less, more preferably 6 or less, and even more preferably 2 or less. For example, 1 to 12 is preferred, more preferably 1 to 6, and even more preferably 1 to 2. By making the number of carbon atoms equal to or less than the upper limit, solubility in a developer is improved and residue tends to be suppressed.

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

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

Examples of the aromatic ring group in ^R5 and ^R6 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, and preferably 12 or less. For example, 4 to 12 is preferred, and 6 to 12 is more preferred. By setting the number of carbon atoms at or above the lower limit, high heat resistance tends to be achieved. By setting the number of carbon atoms at or below the upper limit, solubility in a developer tends to be improved, and residues tend to be suppressed.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence. From the viewpoints of heat resistance and ease of synthesis, a benzene ring or naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

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

From the viewpoint of solubility in a developer, R ⁵ and R ⁶ are each preferably an alkyl group which may have a substituent, and more preferably a methyl group.

( ^R7 )
In the formula (11), R ⁷ represents —SO ³⁻ or —COO ^— . From the viewpoint of brightness, —SO ³⁻ is preferred.

(-CH ₂ - substitution)
In R ¹ to R ⁶ of formula (II), —CH ₂ — contained in the alkyl group, the aromatic ring group, and the hydrocarbon group may be substituted with at least one selected from the group consisting of —O—, —CO—, —COO—, —CONH—, —CONR ⁸ —, —NH—, —NR ⁸ —, —SO ₂ —, —SO ₂ NH—, —SO ₂ NR ⁸ —, and —S—. Of these, —O— and —COO— are preferred from the viewpoints of improving solvent affinity and improving stability over time.
Examples of divalent groups substituted with these groups include _{--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2} O-- and _{--CH.sub.2 CH.sub.2 CH.sub.2 OCO--} .

Examples of ^R8 include an alkyl group which may have a substituent and an aromatic ring group which may have a substituent. From the viewpoint of solvent affinity, an alkyl group which may have a substituent is preferred.
The alkyl group in ^R8 may be a linear, branched, or cyclic alkyl group. The number of carbon atoms is usually 1 or more, preferably 2 or more, and preferably 12 or less, more preferably 6 or less, and even more preferably 3 or less. By making the number of carbon atoms equal to or greater than the lower limit, heat resistance tends to be improved. By making the number of carbon atoms equal to or less than the upper limit, solvent affinity tends to be improved, and stability over time tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 2 to 3 carbon atoms.

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

Examples of the aromatic ring group in ^R8 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, and preferably 12 or less. For example, 2 to 12 is preferred, and 6 to 12 is more preferred. By making the number of carbon atoms equal to or greater than the lower limit, heat resistance tends to be improved. By making the number of carbon atoms equal to or less than the upper limit, solvent affinity tends to be improved, and stability over time tends to be improved.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence. 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 substituents that the aromatic ring group may have include groups described in the substituent group W2 described below.

(Substituent group W1)
halogen atoms such as fluorine atom, chlorine atom, bromine atom, iodine atom, etc.; alkenyl groups having 2 to 8 carbon atoms; alkoxyl groups having 1 to 8 carbon atoms; aromatic hydrocarbon ring groups such as phenyl group, mesityl group, tolyl group, naphthyl group, etc.; cyano group; carboxyl group; acetyloxy group; alkylcarbonyloxy groups having 2 to 9 carbon atoms; sulfamoyl group; alkylsulfamoyl groups having 2 to 9 carbon atoms; alkylcarbonyl groups having 2 to 9 carbon atoms; phenethyl group; hydroxyethyl group; acetylamido group; dialkylaminoethyl groups formed by bonding alkyl groups having 1 to 4 carbon atoms; trifluoromethyl group; trialkylsilyl groups having 1 to 8 carbon atoms; nitro group; alkylthio groups having 1 to 8 carbon atoms.
Preferred are alkoxyl groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, alkylcarboxyl groups having 2 to 8 carbon atoms, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, and fluorine atoms.

(Substituent group W2)
halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 8 carbon atoms; alkenyl groups having 2 to 8 carbon atoms; hydroxyl groups; alkoxy groups having 1 to 8 carbon atoms; aromatic hydrocarbon ring groups such as phenyl group, mesityl group, tolyl group, and naphthyl group; cyano groups; carboxyl groups; acetyloxy groups; alkylcarbonyloxy groups having 2 to 9 carbon atoms; sulfonic acid groups; sulfamoyl groups; alkylsulfamoyl groups having 2 to 9 carbon atoms; carbonyl groups; alkylcarbonyl groups having 2 to 9 carbon atoms; hydroxyethyl groups; acetylamido groups; dialkylaminoethyl groups formed by bonding alkyl groups having 1 to 4 carbon atoms; trifluoromethyl groups; trialkylsilyl groups having 1 to 8 carbon atoms, nitro groups, and alkylthio groups having 1 to 8 carbon atoms.
Preferred are alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, alkylcarboxyl groups having 2 to 8 carbon atoms, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, and fluorine atoms.

(Substituent group W3)
halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkyl groups having 1 to 8 carbon atoms; alkenyl groups having 2 to 8 carbon atoms; alkoxy groups having 1 to 8 carbon atoms; aromatic hydrocarbon ring groups such as phenyl group, mesityl group, tolyl group, and naphthyl group; cyano group; carboxyl group; acetyloxy group; alkylcarbonyloxy groups having 2 to 9 carbon atoms; sulfamoyl group; alkylsulfamoyl groups having 2 to 9 carbon atoms; alkylcarbonyl groups having 2 to 9 carbon atoms; phenethyl group; hydroxyethyl group; acetylamido group; dialkylaminoethyl groups formed by bonding alkyl groups having 1 to 4 carbon atoms; trifluoromethyl group; trialkylsilyl groups having 1 to 8 carbon atoms; nitro group; and alkylthio groups having 1 to 8 carbon atoms.
Preferred are alkoxyl groups having 1 to 8 carbon atoms, cyano groups, acetyloxy groups, alkylcarboxyl groups having 2 to 8 carbon atoms, sulfamoyl groups, alkylsulfamoyl groups having 2 to 9 carbon atoms, and fluorine atoms.

Among the xanthene dyes represented by the general formula (11), the xanthene dyes represented by the following general formula (12) are preferred from the standpoints of heat resistance and brightness.

In formula (12), R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ have the same meanings as R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ in formula (11), respectively.
R ⁹ and R ¹⁰ each independently represent an alkylene group.
However, _-CH2- contained in the alkylene group may be substituted with at least one selected from the group consisting of -O-, -CO-, -COO-, -CONH-, ^-CONR8- , _-NH- , -NR8-, _-SO2- , -SO2NH-, ^-SO2NR8- and _-S- . ^R8 represents an alkyl group which may have a substituent, or an aromatic ring group which may have ^a substituent.

( ^R9 and ^R10 )
In the formula (12), ^R9 and ^R10 each independently represent an alkylene group. The number of carbon atoms in the alkylene group is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 6 or less, and even more preferably 4 or less. By making the number equal to or greater than the lower limit, heat resistance tends to be improved. By making the number equal to or less than the upper limit, solvent affinity tends to be improved, and stability over time tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 2 to 6 carbon atoms, and particularly preferably 3 to 4 carbon atoms.

Examples of alkylene groups include methylene, ethylene, n-propylene, n-butylene, n-pentylene, cyclopentylene, n-hexylene, cyclohexylene, and n-heptylene. From the standpoints of solubility and heat resistance, the n-butylene group is preferred.

The -CH ₂ - contained in the alkylene group may be substituted with at least one selected from the group consisting of -O-, -CO-, -COO-, -CONH-, -CONR 8 -, -NH-, -NR ⁸ -, -SO ₂ -, -SO ₂ NH-, -SO ₂ NR ⁸ -, and -S-. R ⁸ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group. Examples of alkylene groups in which at least one -CH ₂ - is substituted with such a group include _{-CH 2} ^CH ₂ CH ₂ CH ₂ O- and -CH ₂ CH ₂ CH ₂ CH ₂ OCO-. Note that the optionally substituted alkyl group and optionally substituted aromatic ring group for R ⁸ can be those exemplified as R ⁸ in formula (11) above.

Specific examples of xanthene dyes (10) include the following:

Xanthene dye (10) may be a commercially available product, or it may be synthesized using a xanthene dye (e.g., "DCSF" manufactured by Chugai Kasei Co., Ltd.) as the starting material, with reference to JP-A-2013-253168.

(A) The colorant may contain other colorants in addition to dyes. Examples of other colorants include pigments. Among these, when used for green pixel applications, it is preferable to use green pigments, yellow pigments, etc. Furthermore, when used for blue pixel applications, it is preferable to use blue pigments, purple pigments, etc.

Green pigments include C.I. Pigment Green 7, 36, 58, 59, 62, and 63, with C.I. Pigment Green 58 being preferred from the standpoint of brightness.

Examples of yellow pigments include C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127:1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 156 and a 1:1 complex of azobarbituric acid with nickel represented by the following formula (i), or a compound obtained by inserting another compound into a tautomer thereof (hereinafter, sometimes referred to as a "nickel azo complex represented by formula (i)").

Examples of the other compounds include compounds represented by the following formula (ii):

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

Examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

From the standpoint of heat resistance and structural stability, phthalocyanine pigments with a central metal are preferred, with blue copper phthalocyanine pigments being more preferred. Examples of copper phthalocyanine pigments include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, with C.I. Pigment Blue 15:6 being more preferred.

Examples of purple pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
From the viewpoint of heat resistance, purple dioxazine pigments are preferred, and examples of dioxazine pigments include C.I. Pigment Violet 19 and 23, with C.I. Pigment Violet 23 being particularly preferred.

The average primary particle size of the pigment is typically 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 a suitable method for atomizing the pigment.

The content of the colorant (A) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 13% by mass or more, particularly preferably 15% by mass or more, and is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, and particularly preferably 40% by mass or less, based on the total solid content of the colored resin composition. By setting the content at or above the lower limit, a wide range of hues tends to be reproduced. By setting the content at or below the upper limit, stability over time tends to be ensured.
The above upper and lower limits can be combined arbitrarily. For example, although not particularly limited, the content of the colorant (A) in the total solid content of the colored resin composition is preferably 1 to 80 mass%, more preferably 5 to 80 mass%, even more preferably 10 to 60 mass%, even more preferably 13 to 50 mass%, and particularly preferably 15 to 40 mass%.

The content of the dye in the colored resin composition of the present invention is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the colored resin composition. By making the content equal to or greater than the lower limit, brightness tends to be improved. By making the content equal to or less than the upper limit, stability over time tends to be ensured.
The above upper and lower limits can be combined in any combination. For example, the content of the dye in the total solid content of the colored resin composition is preferably 0.5 to 50 mass%, more preferably 0.5 to 40 mass%, even more preferably 1 to 30 mass%, and particularly preferably 1.5 to 20 mass%.

When the colored resin composition of the present invention contains a phthalocyanine dye, its content is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the colored resin composition. By making the content equal to or greater than the lower limit, brightness tends to be improved. By making the content equal to or less than the upper limit, stability over time tends to be ensured.
The above upper and lower limits can be combined in any desired manner. For example, the content of the phthalocyanine dye in the total solid content of the colored resin composition is preferably 1 to 50 mass%, more preferably 3 to 50 mass%, even more preferably 5 to 40 mass%, even more preferably 10 to 30 mass%, and particularly preferably 15 to 20 mass%.

When the colored resin composition of the present invention contains the phthalocyanine dye (1), its content is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, particularly preferably 15% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less, based on the total solid content of the colored resin composition. By making it equal to or greater than the lower limit, brightness tends to be improved. By making it equal to or less than the upper limit, stability over time tends to be ensured.
The above upper and lower limits can be combined in any desired manner. For example, the content of the phthalocyanine dye (1) in the total solid content of the colored resin composition is preferably 1 to 50 mass%, more preferably 3 to 50 mass%, even more preferably 5 to 40 mass%, even more preferably 10 to 30 mass%, and particularly preferably 15 to 20 mass%.

When the colored resin composition of the present invention contains a xanthene dye, its content is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total solid content of the colored resin composition. By making the content equal to or greater than the lower limit, brightness tends to be improved. By making the content equal to or less than the upper limit, stability over time tends to be ensured.
The upper and lower limits can be combined as desired. For example, the content of the xanthene dye in the total solid content of the colored resin composition is preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, even more preferably 1.5 to 10 mass%, and particularly preferably 2 to 5 mass%.

When the colored resin composition of the present invention contains a xanthene dye (10), its content is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 1.5% by mass or more, even more preferably 2% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less, based on the total solid content of the colored resin composition. By making it equal to or greater than the lower limit, brightness tends to be improved. By making it equal to or less than the upper limit, stability over time tends to be ensured.
The upper and lower limits can be arbitrarily combined. For example, the content of the xanthene dye (10) in the total solid content of the colored resin composition is preferably 0.5 to 30 mass%, more preferably 1 to 20 mass%, even more preferably 1.5 to 10 mass%, and particularly preferably 2 to 5 mass%.

When the colored resin composition of the present invention contains other colorants, the content ratio thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, particularly preferably 10% by mass or more, and is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 15% by mass or less, based on the total solid content of the colored resin composition. By setting the content at or above the lower limit, a wide range of hues tends to be reproduced. By setting the content at or below the upper limit, stability over time tends to be ensured.
The above upper and lower limits can be combined in any desired manner. For example, the content of the other colorant in the total solid content of the colored resin composition is preferably 1 to 30 mass%, more preferably 3 to 30 mass%, even more preferably 5 to 25 mass%, even more preferably 7 to 20 mass%, and particularly preferably 10 to 15 mass%.

[1-2] (B) Solvent The (B) solvent has the function of dissolving or dispersing the colorant, alkali-soluble resin, photopolymerization initiator, and other components in the colored resin composition or pigment dispersion of the present invention, and adjusting the viscosity.
The solvent (B) may be any solvent capable of dissolving or dispersing each component.

Such solvents include, for example, glycol monoalkyl ethers such as 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, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and 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, and dipropylene glycol dimethyl ether;
glycol alkyl ether acetates such as 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 ether acetate, and 3-methyl-3-methoxybutyl acetate;

glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diacetate;
alkyl acetates such as cyclohexanol acetate;
ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;
ketones 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, and methoxymethyl pentanone;
monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, and benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Chain or cyclic esters such as 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, butyl 3-methoxypropionate, and γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
ether ketones such as methoxymethylpentanone;
Examples include nitriles such as acetonitrile and benzonitrile.

Commercially available solvents include, for example, mineral spirits, Balsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, and diglyme (all trade names). These solvents may be used alone or in combination.

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

Glycol alkyl ether acetates may be used alone or in combination with other solvents. Glycol monoalkyl ethers are particularly preferred as solvents to be used in combination with glycol alkyl ether acetates. Among these, propylene glycol monomethyl ether is preferred from the viewpoint of solubility of the components in the composition. Glycol monoalkyl ethers are highly polar, and if added in excessive amounts, the pigments tend to aggregate, and the resulting colored resin composition tends to have reduced storage stability, such as an increased viscosity. When glycol monoalkyl ethers are used in combination, the proportion of glycol monoalkyl ethers in the solvent (B) contained in the colored resin composition is preferably 5% to 30% by mass, more preferably 5% to 20% by mass, from the viewpoint of ensuring storage stability.

As another embodiment, a solvent having a boiling point of 150°C or higher is preferred as a solvent to be used in combination with glycol alkyl ether acetates. The use of a solvent having a boiling point of 150°C or higher makes the colored resin composition less likely to dry, thereby preventing the destruction of the interrelationships of the pigment dispersion due to rapid drying. When a solvent having a boiling point of 150°C or higher is used in combination, the content of the solvent having a boiling point of 150°C or higher is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass, of the solvent (B) contained in the colored resin composition. By setting the content at or above the lower limit, it is easy to avoid, for example, the precipitation and solidification of colorant components at the tip of the slit nozzle, which can cause foreign matter defects. By setting the content at or below the upper limit, it is easy to avoid the drying speed of the composition being slow, which can cause problems such as poor tact time in the reduced-pressure drying process and pin marks during pre-baking.
The solvent having a boiling point of 150°C or higher may be either a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, it is not necessary to separately contain a solvent having a boiling point of 150°C or higher.
Preferred examples of solvents having a boiling point of 150° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin.

When forming pixels of a color filter by an inkjet method, the solvent should have a boiling point of typically 130°C or higher and 300°C or lower, preferably 150°C or higher and 280°C or lower. By setting the boiling point at or above the lower limit, the uniformity of the resulting coating film tends to be good. By setting the boiling point at or below the upper limit, the amount of residual solvent remaining during baking tends to be reduced.
The vapor pressure of the solvent used is usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less, from the viewpoint of uniformity of the resulting coating film.

In color filter manufacturing using the inkjet method, the ink ejected from the nozzle is extremely fine, ranging from a few to several tens of picoliters. Therefore, before the ink lands around the nozzle or within the pixel bank, the solvent tends to evaporate, causing the ink to concentrate and dry out. To avoid this, a solvent with a high boiling point is preferred. Specifically, it is preferable to use a solvent with a boiling point of 180°C or higher, more preferably 200°C or higher, and particularly preferably 220°C or higher. Furthermore, the solvent (B) with a boiling point of 180°C or higher, more preferably 200°C or higher, and particularly preferably 220°C or higher, preferably accounts for 50% by mass or more, more preferably 70% by mass or higher, and most preferably 90% by mass or higher of the solvent (B) contained in the colored resin composition. By ensuring that the content is above the lower limit, the effect of preventing solvent evaporation from the droplets tends to be fully demonstrated.

Preferred examples of solvents having a boiling point of 180°C or higher, more preferably 200°C or higher, and particularly preferably 220°C or higher, include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin.
In order to adjust the viscosity of the colored resin composition and the solubility of the solid content, it is also effective to partially contain a solvent having a boiling point of less than 180°C. As the solvent having a boiling point of less than 180°C, a solvent having low viscosity, high solubility, and low surface tension is preferred, and ethers, esters, ketones, etc. are preferred. Among these, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are particularly preferred.

If the solvent contains alcohols, the ejection stability in the inkjet method may be degraded. From the viewpoint of ejection stability in the inkjet method, the alcohol content in the (B) solvent contained in the colored resin composition is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less.

The content of the solvent in the colored resin composition of the present invention is not particularly limited, but is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By setting it to the upper limit or less, it tends to be easier to form a coating film. On the other hand, taking into consideration viscosity suitable for application, it is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more.
The above upper and lower limits can be combined in any combination. For example, the content of the solvent in the colored resin composition of the present invention is 70 to 99% by mass, preferably 75 to 90% by mass, and more preferably 78 to 85% by mass.

[1-3] (C) Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility in a developer.
As the alkali-soluble resin (C), for example, known polymer compounds described in JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, and JP-A-2003-233179 can be used, and among them, the following resins (C-1) to (C-5) are preferred.
(C-1): A resin obtained by adding an unsaturated monobasic acid to at least some of the epoxy groups in a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least some of the hydroxyl groups generated by the addition reaction (hereinafter, this may be referred to as "resin (C-1)").
(C-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter, sometimes referred to as "resin (C-2)")
(C-3) A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter, this may be referred to as "resin (C-3)").
(C-4) (Meth)acrylic resin (hereinafter, may be referred to as “resin (C-4)”)
(C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter, may be referred to as “resin (C-5)”)
Of these, resin (C-1) is particularly preferred.

Resins (C-2) to (C-5) may be any resins that are soluble in an alkaline developer to the extent that the desired development process can be carried out. Resins described in the same section of JP-A-2009-025813 can be preferably used.

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

Examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate glycidyl ether. Of these, glycidyl (meth)acrylate is preferred. One type of epoxy group-containing (meth)acrylate may be used alone, or two or more types may be used in combination.

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

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

The structure represented by general formula (V) is preferably a structure represented by the following formula (Va), (Vb), or (Vc).
By introducing these structures into the alkali-soluble resin, when the colored resin composition of the present invention is used for forming a color filter, the heat resistance of the colored resin composition is improved, and the strength of the pixel formed using the colored resin composition tends to increase.

Mono(meth)acrylates having a structure represented by general formula (V) may be used alone or in combination of two or more.

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

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

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

Other radically polymerizable monomers besides the mono(meth)acrylate represented by general formula (VI) are not particularly limited. For example, styrene; vinyl aromatics substituted with alkyl, nitro, cyano, amide, or ester at the α-, ortho-, meta-, or para-position of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and 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, salicylic (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylate (Meth)acrylic acid esters such as phenethyl (meth)acrylate, cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, Examples of suitable (meth)acrylic acid amides include (meth)acrylic acid N,N-diisopropylamide and (meth)acrylic acid anthracenylamide; vinyl compounds such as (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine and vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N-(4-hydroxyphenyl)maleimide; and N-(meth)acryloylphthalimide.

Among the other radically polymerizable monomers, it is preferable to contain one or more selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimides, from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition. In particular, the content of repeating units derived from one or more selected from the group consisting of styrene, benzyl (meth)acrylate, and monomaleimides is preferably 1 to 70 mol %, and more preferably 3 to 50 mol %, of the repeating units derived from the other radically polymerizable monomers.

The copolymerization reaction of the epoxy group-containing (meth)acrylate with other radically polymerizable monomers can be carried out by a known solution polymerization method. The solvent used is not particularly limited as long as it is inactive in radical polymerization, and any commonly used organic solvent can be used.
For example, 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; propylene glycol monoalkyl ether acetates; acetate esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol esters such as methyl carbitol, ethyl carbitol, and butyl carbitol. Examples of suitable solvents include glycol dialkyl ethers, 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, lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate, dimethylformamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The amount of solvent used is typically 30 to 1,000 parts by weight, and preferably 50 to 800 parts by weight, per 100 parts by weight of the resulting copolymer. Keeping the amount of solvent used within this range tends to make it 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 include known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Examples of organic peroxide catalysts include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide, Examples of peroxides include tert-butyl peroxide, 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-trimethylcyclohexane, and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.

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

The copolymerization reaction can be carried out by dissolving the monomers and radical polymerization initiator used in the copolymerization reaction in a solvent and heating the mixture while stirring; by adding the monomers to which the radical polymerization initiator has been added dropwise to a heated and stirred solvent; or by adding the radical polymerization initiator to a solvent and heating the mixture, followed by adding the monomers dropwise. The reaction conditions can be adjusted depending on the target molecular weight.

As a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, a copolymer consisting of 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth)acrylate and 95 to 10 mol% of repeating units derived from the other radically polymerizable monomer is preferred, a copolymer consisting of 20 to 80 mol% of repeating units derived from the epoxy group-containing (meth)acrylate and 80 to 20 mol% of repeating units derived from the other radically polymerizable monomer is more preferred, and a copolymer consisting of 30 to 70 mol% of repeating units derived from the epoxy group-containing (meth)acrylate and 70 to 30 mol% of repeating units derived from the other radically polymerizable monomer is even more preferred.

By ensuring that the content of repeating units derived from epoxy group-containing (meth)acrylate is at or above the lower limit, the amount of unsaturated monobasic acid or polybasic acid anhydride (described below) added tends to be sufficient. By ensuring that the content of repeating units derived from other radically polymerizable monomers is at or above the lower limit, heat resistance and strength tend to be sufficient.

Next, the epoxy group portion of the copolymer of epoxy resin-containing (meth)acrylate and other radically polymerizable monomers is reacted with 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 acids can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and (meth)acrylic acid substituted at the α-position with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. (Meth)acrylic acid is preferred. One type of unsaturated monobasic acid may be used alone, or two or more types may be used in combination.

By adding an unsaturated monobasic acid, polymerizability can be imparted to the resin (C-1).
The unsaturated monobasic acid is added to typically 10 to 100 mol %, preferably 30 to 100 mol %, more preferably 50 to 100 mol % of the epoxy groups of the copolymer. By adding the unsaturated monobasic acid to the epoxy groups of the copolymer, the colored resin composition tends to have good stability over time. Known methods can be used to add the unsaturated monobasic acid to the epoxy groups of the copolymer.

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, known polybasic acid anhydrides can be used.
Examples of the polybasic acid anhydride include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; and tribasic or higher acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Tetrahydrophthalic anhydride and succinic anhydride are preferred. One type of polybasic acid anhydride may be used alone, or two or more types may be used in combination.

By adding a polybasic acid anhydride, it is possible to impart alkali solubility to the resin (C-1).
The polybasic acid anhydride is added to typically 10 to 100 mol %, preferably 20 to 90 mol %, and more preferably 30 to 80 mol % of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy groups of the copolymer. By setting the addition amount to the upper limit or less, the residual film rate during development tends to be good. By setting the addition amount to the lower limit or more, the solubility tends to be sufficient. Known methods can be used to add the polybasic acid anhydride to the hydroxyl groups.

To improve photosensitivity, a polybasic acid anhydride may be added, and then glycidyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to some of the resulting carboxyl groups. To improve developability, a polybasic acid anhydride may be added, and then a glycidyl ether compound having no polymerizable unsaturated group may be added to some of the resulting carboxyl groups. Either of these may be added.

Examples of glycidyl ether compounds that do not have a polymerizable unsaturated group include glycidyl ether compounds that have a phenyl group or an alkyl group. Commercially available products include those manufactured by Nagase ChemteX Corporation under the trade names "Denacol EX-111," "Denacol EX-121," "Denacol EX-141," "Denacol EX-145," "Denacol EX-146," "Denacol EX-171," and "Denacol EX-192."

The structure of resin (C-1) is described, for example, in Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.

The polystyrene-equivalent weight average molecular weight (Mw) of resin (C-1) measured by GPC is not particularly limited, but is preferably 3,000 to 100,000, and particularly preferably 5,000 to 50,000. Setting it at or above the lower limit tends to result in good heat resistance and film strength. Setting it at or below the upper limit tends to result in good solubility in the developer. As a guide for molecular weight distribution, the weight average molecular weight (Mw)/number average molecular weight (Mn) ratio is preferably 2.0 to 5.0.

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

In formula (I), ^R1 and ^R2 each independently represent a hydrogen atom or a methyl group. * represents a bond.

Among the partial structures represented by formula (I) above, the partial structure represented by the following general formula (I') is preferred from the viewpoints of sensitivity and alkaline developability.

In formula (I'), ^R1 and ^R2 each independently represent a hydrogen atom or a methyl group, and ^Rx represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue refers to a monovalent group obtained by removing one OH group from a polybasic acid or anhydride thereof. 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, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid. One type of polybasic acid may be used alone, or two or more types may be used in combination.
From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferred.

When the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (I), the content of the partial structure represented by the general formula (I) in the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also 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. By setting it to the lower limit or more, the coating film curability upon exposure to ultraviolet light tends to be improved. By setting it to the upper limit or less, the alkali solubility upon alkali development tends to be improved.
The upper and lower limits can be combined in any desired manner. For example, the content of the partial structure represented by general formula (I) in (c1) the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is preferably 10 to 95 mol%, 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%.

When the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (I'), the content of the partial structure represented by the general formula (I') in the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and also 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. By setting it to the lower limit or more, the coating film curability upon exposure to ultraviolet light tends to be improved. By setting it to the upper limit or less, the alkali solubility upon alkali development tends to be improved.
The upper and lower limits can be combined in any desired manner. For example, the content of the partial structure represented by general formula (I) in (c1) the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is preferably 10 to 95 mol%, 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 an acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (I) above, the other partial structures contained therein are not particularly limited. However, from the viewpoint of alkaline solubility during alkaline development, it is also preferable that the resin have a partial structure represented by the following general formula (II), for example.

In the above formula (II), ^R3 represents a hydrogen atom or a methyl group, and ^R4 represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.

(R ⁴ )
In the formula (II), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent.
The alkyl group in ^R4 may be a linear, branched, or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 8 or more, and is 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. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the number of carbon atoms in the alkyl group in ^R4 is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 5 to 14, and particularly preferably 8 to 12.

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

Examples of the aromatic ring group in ^R4 include monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups. The number of carbon atoms is preferably 6 or more, and 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a fused ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a fused ring, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline 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 or a naphthalene ring is preferred, and a benzene ring is more preferred.
Examples of the substituent that the aromatic ring group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkenyl group in ^R4 may be a linear, branched, or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, and is 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. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.

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

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

From the viewpoint of developability and film strength, R ⁴ is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

When the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (II), the content of the partial structure represented by the general formula (II) in the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and particularly preferably 40 mol% or less. By making it equal to or greater than the lower limit, the alkali solubility tends to be improved. By making it equal to or less than the upper limit, the storage stability of the colored resin composition tends to be improved.
The upper and lower limits can be combined in any desired manner. For example, the content of the partial structure represented by general formula (II) in (c1) the acrylic copolymer resin having an ethylenically unsaturated group in a side chain is preferably 1 to 70 mol %, more preferably 5 to 60 mol %, still more preferably 10 to 50 mol %, and particularly preferably 20 to 40 mol %.

(c1) When an acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (I), it is also preferable that the resin further contains a partial structure represented by the following general formula (III), for example, from the viewpoint of improving heat resistance and suppressing brightness reduction.

In the above formula (III), ^R5 represents a hydrogen atom or a methyl group, ^R6 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent, and t represents an integer of 0 to 5.

( ^R6 )
In the formula (III), ^R6 represents an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent.
The alkyl group in ^R6 may be a linear, branched, or cyclic alkyl group. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, and even more preferably 5 or more, and is preferably 20 or less, more preferably 18 or less, more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the number of carbon atoms in the alkyl group in ^R4 is preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, and particularly preferably 5 to 12.

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

The alkenyl group in ^R6 may be a linear, branched, or cyclic alkenyl group. The number of carbon atoms is preferably 2 or more, and is 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. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.

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

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

The alkynyl group in ^R6 may be a linear, branched, or cyclic alkynyl group. The number of carbon atoms is preferably 2 or more, and is 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. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.

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

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

Examples of the halogen atom in ^R6 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of the storage stability of the acrylic copolymer resin, a fluorine atom is preferred.

The alkoxy group in ^R6 may be a linear, branched, or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, and is 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. By setting the number of carbon atoms at or above the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved. By setting the number of carbon atoms at or below the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved.

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

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

The alkyl sulfide group for ^R6 may be a linear, branched, or cyclic alkyl sulfide group. The number of carbon atoms is preferably 1 or more, and is 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. By making the number of carbon atoms equal to or greater than the lower limit, lipophilicity and solubility in solvents tend to be improved. By making the number of carbon atoms equal to or less than the upper limit, hydrophilicity and alkali solubility tend to be improved.

Examples of alkyl sulfide groups include methyl sulfide groups, ethyl sulfide groups, propyl sulfide groups, and butyl sulfide groups. From the standpoint 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, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligoethylene glycol, phenyl, carboxyl, acryloyl, and methacryloyl groups. From the perspective of developability, hydroxy and oligoethylene glycol groups are preferred.

From the viewpoint of developability, R ⁶ is preferably a hydroxyl group or a carboxyl group, and more preferably a carboxyl group.

From the standpoint of ease of manufacturing, it is preferable that t is 0 in formula (III).

When the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (III), the content of the partial structure represented by the general formula (III) in the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 5 mol% or more, particularly preferably 8 mol% or more, and is preferably 50 mol% or less, more preferably 40 mol% or less, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. By setting it to the lower limit or more, heat resistance tends to be improved and brightness reduction tends to be suppressed. By setting it to the upper limit or less, the content of other partial structures increases, and alkali solubility tends to be improved.
The upper and lower limits can be combined in any desired manner. For example, the content of the partial structure represented by the general formula (III) in the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain is preferably 1 to 50 mol %, more preferably 2 to 40 mol %, still more preferably 5 to 30 mol %, and particularly preferably 8 to 20 mol %.

(c1) When an acrylic copolymer resin having an ethylenically unsaturated group in a side chain has a partial structure represented by the general formula (I), it is also preferable that the resin further contains a partial structure represented by the following general formula (IV), for example, from the viewpoint of developability.

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

When the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain contains a partial structure represented by the general formula (IV), the content of the partial structure represented by the general formula (IV) in the (c1) acrylic copolymer resin having an ethylenically unsaturated group in a side chain is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. By making it equal to or greater than the lower limit, the alkali solubility tends to be improved. By making it equal to or less than the upper limit, the storage stability of the colored resin composition tends to be improved.
The upper and lower limits can be combined in any desired manner. For example, the content of the partial structure represented by general formula (IV) in (c1) the acrylic copolymer resin having an ethylenically unsaturated group in its side chain is preferably 5 to 80 mol %, more preferably 10 to 70 mol %, and even more preferably 20 to 60 mol %.

The acid value of the alkali-soluble resin (C) 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, particularly preferably 60 mgKOH/g or more, and is 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. By setting it to the lower limit or more, the alkali solubility tends to be improved. By setting it to the upper limit or less, the storage stability of the colored resin composition tends to be improved.
The above upper and lower limits can be combined in any desired manner. 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, still more preferably 50 to 200 mgKOH/g, and particularly preferably 60 to 150 mgKOH/g.
The acid value represents the number of mg of KOH required to neutralize 1 g of solid content.

The weight average molecular weight (Mw) 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, even more preferably 6,000 or more, still more preferably 7,000 or more, and particularly preferably 8,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 10,000 or less. By making it equal to or greater than the lower limit, heat resistance and coating film curability tend to be improved. By making it equal to or less than the upper limit, alkali solubility tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the weight average molecular weight (Mw) of the alkali-soluble resin (C) is preferably 1,000 to 30,000, more preferably 2,000 to 30,000, even more preferably 4,000 to 20,000, even more preferably 6,000 to 20,000, particularly preferably 7,000 to 15,000, and most preferably 8,000 to 10,000.

The content 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, even more preferably 20% by mass or more, particularly preferably 30% by mass or more, and is preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, particularly preferably 50% by mass or less, based on the total solid content of the colored resin composition. By making it equal to or greater than the lower limit, the curability of the coating film upon exposure to ultraviolet light tends to be improved. By making it equal to or less than the upper limit, the solubility in the developer tends to be improved, and residue tends to be suppressed.
The above upper and lower limits can be combined in any combination. For example, the content of the alkali-soluble resin (C) in the total solid content of the colored resin composition is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, even more preferably 20 to 60 mass%, and particularly preferably 30 to 50 mass%.

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

The photopolymerization initiator (D) in the colored resin composition of the present invention includes a photopolymerization initiator (d1) represented by the following general formula (I) (hereinafter, sometimes referred to as "photopolymerization initiator (d1)"). Because the group bonded to the (keto)oxime ester group of photopolymerization initiator (d1) is a low-reactivity indole ring, the decomposition and reaction speed of the initiator (d1) is slow, allowing for continuous generation of radicals intermittently. This suppresses radical deactivation by the dye, allowing for high curability. Therefore, even in situations where a low prebake temperature results in a large amount of residual solvent and reduced sensitivity, it is believed that penetration of the developer into the coating film can be suppressed, thereby minimizing the impact of changes in prebake temperature on sensitivity.

(In formula (I), R ^d1 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents an aromatic ring group which may have a substituent.

(R ^d1 )
In the formula (I), R ^d1 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group for R ^d1 may be linear, branched, or cyclic, or may be a bonded group thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, even more preferably 5 or less, particularly preferably 3 or less, and most preferably 2 or less, and is usually 1 or more. By setting the number of carbon atoms in the alkyl group to the above upper limit or less, solubility in solvents and ease of synthesis tend to be ensured.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. From the viewpoint of ease of synthesis, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is even more preferred.
Examples of the substituent that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a halogen atom such as F, Cl, Br, or I, and a hydroxyl group. From the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferred. From the viewpoint of sensitivity, an unsubstituted alkyl group is preferred.

Examples of the aromatic ring group in R ^d1 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, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By setting the number of carbon atoms of the aromatic ring group to the above lower limit or more, the molecule tends to be stable. By setting it to the above upper limit or less, the solvent solubility tends to be good.
The above upper and lower limits can be combined in any combination. For example, the aromatic hydrocarbon ring group and aromatic heterocyclic group preferably have 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence.
From the viewpoint of solvent solubility, 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 substituents that the aromatic ring group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, and nitro groups. From the perspective of solvent solubility, alkoxy groups having 1 to 3 carbon atoms and hydroxyl groups are preferred.

From the viewpoints of solubility in solvents and ease of synthesis, R ^d1 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, further preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

(R ^d2 )
In the formula (I), R ^d2 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group for R ^d2 may be linear, branched, or cyclic, or may be a combination of these. From the viewpoint of solvent solubility, linear or branched is preferred, and linear is more preferred. From the viewpoint of sensitivity, an unsubstituted linear alkyl group is preferred.

The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and preferably 12 or less, more preferably 10 or less, even more preferably 9 or less, particularly preferably 8 or less. By setting the number of carbon atoms in the alkyl group to the above lower limit or more, sensitivity tends to be improved. By setting it to the above upper limit or less, solvent affinity tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 2 to 12, even more preferably 3 to 10, still more preferably 4 to 10, particularly preferably 5 to 9, and most preferably 6 to 8.

Examples of substituents that the alkyl group may have include aromatic ring groups having 6 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, alkoxycarbonyl groups having 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, and hydroxyl groups. From the perspective of solvent solubility, alkoxy groups having 1 to 3 carbon atoms are preferred. From the perspective of ease of synthesis, unsubstituted groups are preferred.

Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. From the standpoints of sensitivity and solvent affinity, propyl, butyl, pentyl, and hexyl groups are preferred, pentyl and hexyl groups are more preferred, and hexyl groups are even more preferred.

Examples of the aromatic ring group in R ^d2 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, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By setting the number of carbon atoms of the aromatic ring group to the above lower limit or more, the molecule tends to be stable. By setting it to the above upper limit or less, the solvent solubility tends to be good.
The above upper and lower limits can be combined in any combination. For example, the number of carbon atoms in the aromatic hydrocarbon ring group and aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence.
From the viewpoint of solvent solubility, 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 substituents that the aromatic ring group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, and nitro groups. The alkyl chain portion of the substituent may be linear or branched, and may further have substituents such as alkoxy groups having 1 to 3 carbon atoms, alkylthio groups having 1 to 3 carbon atoms, halogen atoms, hydroxyl groups, and nitro groups. From the standpoint of solvent solubility, alkoxy groups having 1 to 5 carbon atoms and hydroxyl groups are preferred.

From the viewpoint of solvent affinity and sensitivity, R ^d2 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, further preferably a butyl group, a pentyl group, or a hexyl group, and particularly preferably a hexyl group.

(R ^d3 )
In the formula (I), R ^d3 represents an aromatic ring group which may have a substituent.

Examples of the aromatic ring group in R ^d3 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms therein is usually 4 or more, preferably 6 or more, and preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. By making the number of carbon atoms in the aromatic ring group equal to or greater than the lower limit, sensitivity during exposure tends to be improved. By making the number of carbon atoms equal to or less than the upper limit, solvent affinity tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the number of carbon atoms in the aromatic hydrocarbon ring group and aromatic heterocyclic group is preferably 4 to 12, more preferably 4 to 10, and even more preferably 6 to 8.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring, each having one free valence.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a condensed ring.Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazoline ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring, each of which has one free valence.
From the viewpoint of solvent affinity, 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 substituents that the aromatic ring group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, aryloxy groups having 6 to 10 carbon atoms, aryloyl groups having 6 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, hydroxyl groups, and nitro groups. From the perspective of sensitivity during exposure, aryl groups having 6 to 10 carbon atoms and aryloyl groups having 6 to 10 carbon atoms are preferred.

From the viewpoints of solvent affinity and sensitivity during exposure, R ^d3 is preferably an aromatic hydrocarbon group having one free valence and which may have a substituent, and more preferably an aromatic hydrocarbon group having one free valence and which may have a substituent.

(p)
In the formula (I), from the viewpoint of sensitivity, p is preferably 0. In the formula (I), from the viewpoint of suppressing residues by improving solvent affinity, p is preferably 1.

Among the photopolymerization initiators (d1), photopolymerization initiators represented by the following general formula (II) are preferred from the standpoints of solvent affinity and sensitivity during exposure.

In formula (II), R ^d1 , R ^d2 and p have the same meanings as in formula (I).
R ^d4 represents any monovalent substituent, and q represents an integer of 0 to 3.

(R ^d4 )
In the formula (II), R ^d4 represents any monovalent substituent.
Examples of the optional monovalent substituent 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; halogen atoms such as F, Cl, Br, and I; acyl groups having 1 to 10 carbon atoms; alkyl ester groups having 1 to 10 carbon atoms; alkoxycarbonyl groups having 1 to 10 carbon atoms; halogenated alkyl groups having 1 to 10 carbon atoms; aromatic ring groups having 4 to 10 carbon atoms; amino groups; aminoalkyl groups having 1 to 10 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Examples of the substituents that the benzoyl and thenoyl groups may have include alkyl groups having 1 to 3 carbon atoms and alkoxy groups having 1 to 3 carbon atoms, and these may be present in a range of 0 to 3. From the viewpoint of sensitivity, nitro groups, cyano groups, optionally substituted benzoyl groups, and optionally substituted thenoyl groups are preferred, with benzoyl groups being more preferred.
In R ^d4 , when q is 2 or greater, multiple R ^d4 s may be bonded together to form a ring, which may be an aliphatic ring or an aromatic ring.
The substitution position of R ^d4 is not particularly limited and may be any of the o-position, m-position and p-position, but from the viewpoints of solvent affinity and sensitivity, the p-position is preferred.

(q)
In the formula (I), q is preferably 0 or 1, and more preferably 1, from the viewpoint of suppressing residues due to improved solubility in a solvent and improving sensitivity during exposure.

The method for producing the photopolymerization initiator (d1) is not particularly limited, but it can be produced, for example, by the method described in JP 2017-179211 A.

Specific examples of photopolymerization initiator (d1) include the following:

The photopolymerization initiator (D) may further contain another photopolymerization initiator (d2) in addition to the photopolymerization initiator (d1).
Other examples of the photopolymerization initiator (d2) include titanocene derivatives containing titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described in JP-A-2000-56118; halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives; and oxime ester derivatives described in JP-A-2000-80068 and JP-A-2006-36750.

Examples of titanocene derivatives include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl-1-yl), and dicyclopentadienyltitanium [2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl].

Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Examples of halomethyl-s-triazine derivatives include 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, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

Examples of oxime ester derivatives include the oxime ester compounds described in JP-A Nos. 2004-534797, 2000-80068, 2006-36750, 2008-179611, 2012-526185, and 2012-519191. From the viewpoint of sensitivity, methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate is preferred. Preferred examples of product names include OXE-01, OXE-02, OXE-03, and OXE-04 (manufactured by BASF), TR-PBG-304, TR-PBG-305, and TR-PBG314 (manufactured by Changzhou Strong Industry Co., Ltd.), and NCI-831 and NCI-930 (manufactured by ADEKA Corporation).
The other photopolymerization initiators (d2) may be used alone or in combination of two or more.

(D) The photopolymerization initiator may be used alone or in a mixture of two or more types.

In addition to the photopolymerization initiator (D), a chain transfer agent may be used. The chain transfer agent is a compound that has the function of receiving the generated radicals and transferring the radicals to another compound.
As the chain transfer agent, various compounds having the above functions can be used. Examples of chain transfer agents include mercapto group-containing compounds and carbon tetrachloride. It is more preferable to use a compound having a mercapto group because it tends to have a high chain transfer effect. This is thought to be because the small S-H bond energy makes bond cleavage more likely to occur, and hydrogen abstraction reactions and chain transfer reactions are more likely to occur. It is effective in improving sensitivity and surface curing properties.

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

Among mercapto group-containing compounds with aromatic rings, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred. Among aliphatic mercapto group-containing compounds, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are preferred.

In terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, such as trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), and 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, with pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) being more preferred.

A variety of these can be used alone or in a mixture of two or more.

In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 0.5% by mass or more, more preferably 0.8% by mass or more, even more preferably 1.0% by mass or more, particularly preferably 1.2% by mass or more, and is preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably 8% by mass or less, particularly preferably 7% by mass or less, based on the total solid content of the colored resin composition. By making it equal to or greater than the lower limit, the curability of the coating film tends to be improved. By making it equal to or less than the upper limit, visible light absorption is reduced, and brightness tends to be improved.
The above upper and lower limits can be combined in any combination. For example, the content of the (D) photopolymerization initiator in the total solid content of the colored resin composition is preferably 0.5 to 10 mass%, more preferably 0.8 to 9 mass%, even more preferably 1.0 to 8 mass%, and particularly preferably 1.2 to 7 mass%.

In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (d1) is not particularly limited, but is preferably 0.5 mass% or more, more preferably 0.8 mass% or more, even more preferably 1.0 mass% or more, particularly preferably 1.2 mass% or more, and is preferably 7 mass% or less, more preferably 5 mass% or less, even more preferably 4 mass% or less, particularly preferably 3 mass% or less, based on the total solid content of the colored resin composition. By making it equal to or greater than the lower limit, the coating film curability during low-temperature pre-baking tends to be improved. By making it equal to or less than the upper limit, visible light absorption is reduced, and brightness tends to be improved.
The upper and lower limits can be combined in any combination. For example, the content of the photopolymerization initiator (d1) in the total solid content of the colored resin composition is preferably 0.5 to 7 mass%, more preferably 0.8 to 5 mass%, even more preferably 1.0 to 4 mass%, and particularly preferably 1.2 to 3 mass%.

[1-5] Other Solid Contents The colored resin composition of the present invention may further contain solid components other than the above-described components, as necessary. Examples of such components include photopolymerizable monomers, dispersants, dispersing aids, surfactants, and antioxidants.

[1-5-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as an "ethylenic compound") is preferred. The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and hardening by the action of a photopolymerization initiator when the colored resin composition of the present invention is irradiated with actinic rays. Note that the term "monomer" in the present invention refers to a concept that is opposite to so-called polymeric substances, and refers to a concept that includes not only monomers in the narrow sense but also dimers, trimers, and oligomers.
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 in the polyfunctional ethylenic monomer is not particularly limited, but is usually two or more, preferably four or more, more preferably five or more, and preferably eight or less, more preferably seven or less. By setting the number to be equal to or greater than the lower limit, high sensitivity tends to be obtained. By setting the number to be equal to or less than the upper limit, solubility in solvents tends to be improved.

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, esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, esters obtained by esterification of unsaturated carboxylic acids and polyvalent hydroxy compounds such as the aforementioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, and ethylenic compounds having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth)acryloyl-containing hydroxy compound.

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Other examples include methacrylic acid esters in which the acrylic acid portion of these acrylates is replaced with a methacrylic acid portion, itaconic acid esters in which the itaconic acid portion is replaced, crotonic acid esters in which the crotonic acid portion is replaced, and maleic acid esters in which the maleic acid portion is replaced.

Examples of the esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polycarboxylic acid and a polyhydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include a condensate of acrylic acid, phthalic acid, and ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol, and glycerin.

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

Other useful ethylenic compounds for use in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate.
The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, a polyfunctional monomer obtained by reacting an unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give an acid group, and particularly preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, a polyfunctional monomer obtained by reacting an unreacted hydroxyl group of pentaerythritol and/or dipentaerythritol with a non-aromatic carboxylic acid anhydride to give an acid group.

These monomers may be used alone, but since it is difficult to use a single compound in the production, two or more of them may be used in combination.
If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. By setting the acid value at or above the lower limit, the development solubility characteristics tend to be good. By setting the acid value at or below the upper limit, production and handling tend to be good, and curing properties such as photopolymerization performance and pixel surface smoothness tend to be good. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, it is preferable to adjust the acid group content of the polyfunctional monomer as a whole to fall within the above range.

In the present invention, a more preferred polyfunctional monomer having an acid group is a mixture primarily composed of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, commercially available as TO1382 from Toagosei Co., Ltd. This polyfunctional monomer can also be used in combination with other polyfunctional monomers. Furthermore, the polyfunctional monomers described in paragraphs [0056] and [0057] of JP 2013-140346 A can also be used.

In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of pixel edges, it is preferable to use the polymerizable monomers described in JP 2013-195971 A. From the viewpoint of achieving both high sensitivity of the coating film and a shorter development time, it is preferable to use the polymerizable monomers described in JP 2013-195974 A.

When the colored resin composition of the present invention contains a photopolymerizable monomer, the content of the photopolymerizable monomer is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, even more preferably 10% by mass or more, particularly preferably 12% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, particularly preferably 40% by mass or less, based on the total solid content of the colored resin composition. By making the content equal to or greater than the lower limit, the curability of the coating film tends to be improved. By making the content equal to or less than the upper limit, the flatness of the coating film surface tends to be ensured.
The above upper and lower limits can be combined in any combination. For example, the content of the photopolymerizable monomer in the total solid content of the colored resin composition is preferably 5 to 60 mass%, more preferably 8 to 50 mass%, even more preferably 10 to 45 mass%, and particularly preferably 12 to 40 mass%.

[1-5-2] Dispersant, Dispersing 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 polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic-modified polyester-based dispersants. Examples of these dispersants include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemicals), SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), and Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), as well as those described in JP 2013-119568 A.

Among the polymer dispersants, from the viewpoint of dispersibility and storage stability, a block copolymer having a functional group containing a nitrogen atom is preferred, and an acrylic block copolymer is more preferred.
The block copolymer having a functional group containing a nitrogen atom is preferably an A-B block copolymer and/or a B-A-B block copolymer consisting of an A block having a quaternary ammonium base and/or an amino group in the side chain and a B block not having a quaternary ammonium base and/or an amino group.

Examples of the functional group containing a nitrogen atom include primary, secondary, or tertiary amino groups and quaternary ammonium salt groups. From the viewpoints of dispersibility and storage stability, it is preferable for the functional group to have a primary, secondary, or tertiary amino group, and it is more preferable for the functional group to have a tertiary amino group.
The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, it is preferably a repeating unit represented by the following general formula (1):

In the above formula (1), ^R1 and ^R2 each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and ^R1 and ^R2 may be bonded to each other to form a cyclic structure. ^R3 represents a hydrogen atom or a methyl group. X represents a divalent linking group.

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

In the above formula (1), the number of carbon atoms in the aryl group, which may have a substituent, is not particularly limited, but is typically 6 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 8 or less. Examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, and anthracenyl groups. Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, and diethylphenyl groups are preferred, and phenyl, methylphenyl, and ethylphenyl groups are more preferred.

In the above formula (1), the number of carbon atoms in the aralkyl group, which may have a substituent, is not particularly limited, but is typically 7 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. Examples of aralkyl groups include phenylmethyl, phenylethyl, phenylpropyl, phenylbutyl, and phenylisopropyl groups, with phenylmethyl, phenylethyl, phenylpropyl, and phenylbutyl groups being preferred, and phenylmethyl and phenylethyl groups being more preferred.

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

Examples of substituents that the alkyl group, aralkyl group, or aryl group in the above formula (1) may have include halogen atoms, alkoxy groups, benzoyl groups, and hydroxyl groups, and from the perspective of ease of synthesis, it is preferable that they are unsubstituted.

In the above formula (1), the cyclic structure formed by bonding ^R1 and ^R2 to each other includes, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a fused ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that is not aromatic, and is more preferably a saturated ring. Specific examples include the nitrogen-containing heterocycle of the following formula (IV):

These cyclic structures may further have substituents.

In the above formula (1), examples of the divalent linking group X include an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ¹³ - group, and a -COOR ¹⁴ - group (wherein R ¹³ and R ¹⁴ are single bonds, alkylene groups having 1 to 10 carbon atoms, or ether groups (alkyloxyalkyl groups) having 2 to 10 carbon atoms), and a -COO-R ¹⁴ - group is preferred.

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

It is preferable that the block copolymer has a repeating unit represented by the following formula (2), from the viewpoint of increasing compatibility with binder components such as solvents and improving dispersion stability.

In the above formula (2), 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 of the alkyl group, which may have a substituent, in R ¹¹ of the above formula (2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less.
The above upper and lower limits can be combined in any combination. For example, the alkyl group in R ¹¹ of the above formula (2) preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, with a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group being preferred, and a methyl group, an ethyl group, a propyl group, and a butyl group being more preferred. The alkyl group in ^R11 of the above formula (2) may be either linear or branched. The alkyl group in ^R11 of the above formula (2) may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.
Examples of the substituent that the alkyl group in R ¹¹ of the above formula (2) may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, and from the viewpoint of ease of synthesis, it is preferably unsubstituted.

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

The content of the repeating unit represented by formula (2) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less.
The upper and lower limits can be combined arbitrarily. For example, the content of the repeating unit represented by formula (2) in all repeating units of the block copolymer is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and even more preferably 4 to 10 mol%. Within the above ranges, compatibility with binder components such as solvents and dispersion stability tend to be compatible.

Furthermore, it is preferable that the block copolymer has a repeating unit represented by the following formula (3), from the viewpoint of increasing compatibility with binder components such as solvents and improving dispersion stability.

In the above formula (3), ^R8 is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and ^R9 is a hydrogen atom or a methyl group.

The number of carbon atoms in the alkyl group, which may have a substituent, in ^R8 of the above formula (3) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Methyl, ethyl, propyl, butyl, pentyl, and hexyl groups are preferred, and methyl, ethyl, propyl, and butyl groups are more preferred. The alkyl group in ^R8 of the above formula (3) may be either linear or branched. The alkyl group in ^R8 of the above formula (3) may include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group, which may have a substituent, in ^R8 of the above formula (3) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and more preferably 12 or less. 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, with a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group being preferred, and a phenyl group, a methylphenyl group, and an ethylphenyl group being more preferred.

The number of carbon atoms in the aralkyl group which may have a substituent in ^R8 of the above formula (3) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and more preferably 12 or less. Examples of the aralkyl group include a phenylmethyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, with a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group being preferred, and a phenylmethyl group and a phenylethyl group being more preferred.

From the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group.
Examples of the substituent that the alkyl group in ^R8 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 ^R8 includes both linear and branched chain alkyl groups.

The content of the repeating unit represented by formula (3) in all repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more, and is preferably 80 mol% or less, more preferably 70 mol% or less.
The upper and lower limits can be arbitrarily combined. For example, the content of the repeating unit represented by formula (3) in all repeating units of the block copolymer is preferably 30 to 80 mol %, more preferably 40 to 80 mol %, and even more preferably 50 to 70 mol %. Within the above range, dispersion stability and high brightness tend to be compatible.

The block copolymer may have repeating units other than the repeating units represented by general formula (1), the repeating units represented by general formula (2), and the repeating units represented by general formula (3). Examples of such repeating units include repeating units derived from styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether; crotonate glycidyl ether; and N-methacryloylmorpholine.

From the viewpoint of further enhancing dispersibility, the block copolymer is preferably a block copolymer having an A block having a repeating unit represented by general formula (1) and a B block not having a repeating unit represented by general formula (1), and is more preferably an A-B block copolymer or a B-A-B block copolymer. The B block preferably has a repeating unit represented by general formula (2) and a repeating unit represented by general formula (3).

The A block may contain repeating units other than the repeating units represented by general formula (1). Examples of such repeating units include repeating units derived from the (meth)acrylic acid ester monomers described above. The content of repeating units other than the repeating units represented by general formula (1) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %. It is most preferable that the A block does not contain repeating units other than the repeating units represented by general formula (1).

The B block may contain repeating units other than the repeating units represented by general formula (2) and the repeating units represented by general formula (3). Examples of such repeating units include repeating units derived from styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide-based monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonate glycidyl ether; and N-methacryloylmorpholine. The content of repeating units other than the repeating units represented by general formula (2) and the repeating units represented by general formula (3) in the B block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %. It is most preferred that the B block does not contain repeating units other than the repeating units represented by general formula (2) and the repeating units represented by general formula (3).

From the standpoint of dispersibility, it is preferable that the acid value of the block copolymer is low, and it is particularly preferable that it is 0 mg KOH/g.

From the viewpoint of dispersibility and developability, the amine value of the block copolymer is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, even more preferably 90 mgKOH/g or more, particularly preferably 100 mgKOH/g or more, and most preferably 105 mgKOH/g or more, and is preferably 150 mgKOH/g or less, more preferably 130 mgKOH/g or less.
The above upper and lower limits can be combined in any desired manner. For example, the amine value of the block copolymer is preferably 30 to 150 mgKOH/g, more preferably 50 to 150 mgKOH/g, even more preferably 70 to 150 mgKOH/g, still more preferably 90 to 130 mgKOH/g, particularly preferably 100 to 130 mgKOH/g, and most preferably 105 to 130 mgKOH/g.
The amine value represents the amine value calculated as the effective solid content, and is a value expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content.

The molecular weight of the block copolymer is preferably in the range of 1,000 to 30,000 in weight average molecular weight (Mw). When it is within this range, dispersion stability is improved and drying foreign matter tends to be less likely to be generated when applying using the slit nozzle method.

The block copolymer can be produced by known methods. For example, it can be produced by living polymerization of the monomers that introduce the above-mentioned repeating units. Examples of living polymerization methods include those described in Japanese Patent Application Laid-Open Nos. 9-62002 and 2002-31713, P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al., Macromolecules, 14, 1601 (1981), and K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Migite and Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura and Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida and Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Hertler et al., Macromolecules, 20, 1473 (1987), and the like can be used.

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, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 10% by mass or less, based on the total solid content of the colored resin composition. By making the content equal to or greater than the lower limit, dispersibility and storage stability tend to be improved. By making the content equal to or less than the upper limit, electrical reliability and developability tend to be improved.
The above upper and lower limits can be combined in any combination. For example, the content of the dispersant in the total solid content of the colored resin composition is preferably 0.001 to 25 mass%, more preferably 0.01 to 20 mass%, even more preferably 0.1 to 15 mass%, and particularly preferably 1 to 10 mass%.

[0044] When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and is preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the pigment.
The upper and lower limits can be combined in any desired manner. For example, the content of the dispersant relative to 100 parts by mass of the pigment is preferably 0.5 to 70 parts by mass, more preferably 5 to 70 parts by mass, even more preferably 10 to 50 parts by mass, even more preferably 15 to 40 parts by mass, and particularly preferably 20 to 30 parts by mass. By keeping the content within the above ranges, it tends to be possible to obtain a colorable resin composition that is excellent in dispersion stability and has high brightness.

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

[1-5-3] Surfactant When the colored resin composition of the present invention contains a surfactant, various surfactants can be used, such as anionic, cationic, nonionic, amphoteric surfactants, etc. Nonionic surfactants are preferred because they are less likely to adversely affect the properties of the colored resin composition of the present invention.
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 mass% or more, preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 0.1 mass% or more, and is usually 10 mass% or less, preferably 1 mass% or less, even more preferably 0.5 mass% or less, particularly preferably 0.3 mass% or less, based on the total solid content of the colored resin composition.
The above upper and lower limits can be combined in any combination. For example, the content of the surfactant in the total solid content of the colored resin composition is preferably 0.001 to 10 mass%, more preferably 0.01 to 1 mass%, even more preferably 0.05 to 0.5 mass%, and particularly preferably 0.1 to 0.3 mass%.

[2] Preparation of Colored Resin Composition When preparing a colored resin composition containing a pigment as a colorant, the pigment, solvent, and dispersant are weighed in predetermined amounts, and the pigment-containing colorant is dispersed in a dispersion treatment step to prepare a pigment dispersion. As described above, in the dispersion treatment step, it is preferable to use, for example, a dispersing aid and/or a dispersing resin in combination.
In the dispersion treatment step, for example, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, or a homogenizer can be used. This dispersion treatment microparticulates the colorant, improving the coating properties of the colored resin composition and improving the transmittance of pixels in the finished color filter substrate. When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm.

The temperature during dispersion treatment is usually set to a range of 0°C or higher, preferably room temperature or higher, and usually 100°C or lower, preferably 80°C or lower. For example, it can be set to 0-100°C, 0-80°C, or room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the pigment dispersion and the size of the sand grinder device, so it can be adjusted as appropriate.

The pigment dispersion obtained in the dispersion process is mixed with a solvent, alkali-soluble resin, photopolymerization initiator, and other components as needed to produce a uniform dispersion. Note that since fine particles of dust may become mixed in during the dispersion and mixing processes, it is preferable to filter the resulting pigment dispersion using a filter or similar.

When preparing a colored resin composition that does not contain a pigment as a colorant, a homogeneous solution can be obtained by mixing the colorant, solvent, alkali-soluble resin, photopolymerization initiator, and, if necessary, other components. It is preferable to filter the resulting solution using a filter or the like.

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

[3-1] Transparent substrate (support)
The transparent substrate of the color filter may be made of any material, as long as it is transparent and has adequate strength. Examples include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass. From the viewpoint of heat resistance, glass and heat-resistant resins are preferred.

To improve surface properties such as adhesion, the transparent substrate and the black matrix-formed substrate may be subjected to, as needed, corona discharge treatment, ozone treatment, or thin-film formation treatment using silane coupling agents or various resins such as urethane-based resins. The thickness of the transparent substrate is typically 0.05 mm or more, preferably 0.1 mm or more, and typically 10 mm or less, preferably 7 mm or less, e.g., 0.05 to 10 mm, 0.1 to 10 mm, 0.05 to 7 mm, or 0.1 to 7 mm. Furthermore, when a thin-film formation treatment using various resins is performed, the film thickness is typically 0.01 μm or more, preferably 0.05 μm or more, and typically 10 μm or less, preferably 5 μm or less, e.g., 0.01 to 10 μm, 0.05 to 10 μm, 0.01 to 5 μm, or 0.05 to 5 μm.

[3-2] Black Matrix The color filter of the present invention can be produced by providing a black matrix on the above-mentioned transparent substrate and then forming pixel images, usually red, green, and blue. Of the red, green, and blue pixels, the colored resin composition of the present invention is preferably used as a coating liquid for forming green or blue pixels (resist pattern). A pixel image is formed by applying a coating liquid for forming a resist pattern containing the colored resin composition of the present invention onto a surface on which a resin black matrix has been formed on a transparent substrate, or onto a surface on which a metal black matrix has been formed using a light-shielding metal material, followed by heat drying, image exposure, development, and heat curing.

The black matrix is formed on a transparent substrate using a light-shielding metal material or a colored resin composition for a black matrix. Examples of the light-shielding metal material include chromium compounds such as metallic chromium, chromium oxide, and chromium nitride, and nickel-tungsten alloys, and these may be laminated in multiple layers.
The light-shielding metal thin film is generally formed by a sputtering method. After forming a desired pattern in a film using a positive photoresist, the film is etched using an etching solution consisting of a mixture of ceric ammonium nitrate and perchloric acid and/or nitric acid for chromium compounds, or an etching solution appropriate for the material for other materials. The positive photoresist is then stripped off with a dedicated stripper to form a black matrix.

For example, a thin film of a light-shielding metal material is formed on a transparent substrate by vapor deposition or sputtering. Next, a coating film of a colored resin composition is formed on this light-shielding metal thin film, and the coating film is exposed and developed using a photomask with a repeating pattern such as stripes, mosaics, or triangles to form a resist image. The coating film can then be etched to form a black matrix.

When using a photosensitive colored resin composition for a black matrix, a black matrix is formed using a colored resin composition containing a black colorant. For example, a colored resin composition containing a single or multiple black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, or titanium black, or a mixture of red, green, blue, or other colors appropriately selected from inorganic or organic pigments and dyes, can be used to form the black matrix in the same manner as the method for forming red, green, and blue pixel images described below.

[3-3] Formation of Pixels A colored resin composition of one of red, green, and blue colors is applied onto a transparent substrate provided with a black matrix, and after drying, a photomask is placed on the coating film, and a pixel image is formed by image exposure through the photomask, development, and, if necessary, heat curing or photocuring. This operation is performed for each of the three colored resin compositions of red, green, and blue, thereby forming a color filter image.

The colored resin composition for color filters can be applied by, for example, the spinner method, wire bar method, flow coating method, die coating method, roll coating method, or spray coating method. The die coating method is preferable from an overall perspective, as it significantly reduces the amount of coating liquid used, is completely free of the mist that can adhere when using spin coating, and suppresses the generation of foreign matter.

The thickness of the coating film, as measured after drying, is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less. By setting the thickness at or above the lower limit, it becomes easier to increase the pigment concentration, making it easier to achieve the desired color expression. By setting the thickness at or below the upper limit, it becomes easier to facilitate pattern development, and it becomes easier to facilitate gap adjustment in the liquid crystal cell fabrication process.
The above upper and lower limits can be combined in any desired manner. For example, the thickness of the coating film is preferably 0.2 to 20 μm, more preferably 0.5 to 10 μm, and even more preferably 0.8 to 5 μm.

[3-4] Drying of the coating film Drying (pre-baking) of the coating film after applying the colored resin composition to the transparent substrate can be performed by, for example, a drying method using a hot plate, an IR oven, a convection oven, or the like, or a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
In general, in a drying method using a hot plate, an IR oven, a convection oven, or the like, the material is pre-dried and then re-heated for redrying.
The conditions for pre-drying can be selected depending on the type of solvent component, the performance of the dryer to be used, and the like.
The drying temperature for the preliminary drying is usually 40°C or higher, preferably 50°C or higher, and usually 80°C or lower, preferably 70°C or lower, for example, 40 to 80°C, 40 to 70°C, 50 to 80°C, or 50 to 70°C.
The drying time for the preliminary drying is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less, for example, 15 seconds to 5 minutes, 30 seconds to 5 minutes, 15 seconds to 3 minutes, or 30 seconds to 3 minutes.

The temperature condition for re-drying is preferably higher than the temperature for pre-drying.
The drying temperature for re-drying is usually 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, particularly preferably 130°C or lower, for example, 50 to 200°C, 50 to 160°C, 50 to 130°C, 70 to 200°C, 70 to 160°C, or 70 to 130°C.
The drying time for re-drying varies depending on the heating temperature, but is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes or less, for example, 10 seconds to 10 minutes, 15 seconds to 10 minutes, 10 seconds to 5 minutes, or 15 seconds to 5 minutes.
If the drying temperature is equal to or lower than the upper limit, sufficient adhesion to the transparent substrate is obtained, while thermal polymerization due to decomposition of the binder resin is unlikely to be induced, and development defects are unlikely to occur.

[3-5] Exposure Step Imagewise exposure is performed by superimposing a negative matrix pattern on a coating film of the colored resin composition and irradiating the film with a light source of ultraviolet or visible light through this mask pattern. If necessary, to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen-blocking layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer before exposure. The light source used for the imagewise exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, as well as laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. When using light of a specific wavelength, an optical filter can also be used.

[3-6] Development Step The color filter of the present invention can be produced by imagewise exposing a coating film using the colored resin composition of the present invention to the light source described above, and then developing the film using an aqueous solution containing a surfactant and an alkaline compound to form an image 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 inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, and ammonium hydroxide; and organic alkaline compounds such as mono-, di-, or triethanolamine, mono-, di-, or trimethylamine, mono-, di-, or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di-, or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. These alkaline compounds may be used alone or in combination.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; anionic surfactants such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate 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. The organic solvent may be used in combination with an aqueous solution.
The conditions for the development treatment are not particularly limited, but the development temperature is usually 10° C. or higher, preferably 15° C. or higher, more preferably 20° C. or higher, and usually 50° C. or lower, preferably 45° C. or lower, more preferably 40° C. or lower, for example, 10 to 50° C., 10 to 45° C., 10 to 40° C., 15 to 50° C., 15 to 45° C., 15 to 40° C., 20 to 50° C., 20 to 45° C., or 20 to 40° C. The development method can be any method such as immersion development, spray development, brush development, or ultrasonic development.

[3-7] Heat Curing Treatment After development, the color filter is subjected to a heat curing treatment.
The temperature in the heat curing treatment is usually 100°C or higher, preferably 150°C or higher, and usually 280°C or lower, preferably 250°C or lower, for example, 100 to 280°C, 100 to 250°C, 150 to 280°C, or 150 to 250°C.
The time for the heat curing treatment is in the range of 5 minutes to 60 minutes.
After going through this series of steps, the formation of a patterned image of one color is completed. These steps are repeated in order to 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 order described above.

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

[4] Image display device (panel)
The image display device of the present invention has the color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic EL display device.

[4-1] Liquid Crystal Display Device A liquid crystal display device can be manufactured by forming an alignment film on the color filter of the present invention, dispersing spacers on the alignment film, and then bonding it to an opposing substrate to form a liquid crystal cell. Liquid crystal is then injected into the formed liquid crystal cell, and the cell is connected to the opposing electrode. A resin film such as polyimide is suitable for the alignment film. Gravure printing and/or flexographic printing are typically used to form the alignment film, and the thickness of the alignment film is several tens of nanometers. After hardening the alignment film by thermal baking, the surface is treated by ultraviolet irradiation or treatment with a rubbing cloth to create a surface state that allows adjustment of the tilt of the liquid crystal.

Spacers are used in sizes that correspond to the gap (gap) with the opposing substrate, and are typically 2 to 8 μm. Transparent resin film photospacers can be formed on the color filter substrate using photolithography and used in place of spacers. An array substrate is typically used as the opposing substrate, with thin-film transistor substrates being particularly suitable.

The gap between the opposing substrate and the substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm to 8 μm. After bonding with the opposing substrate, the area other than the liquid crystal injection port is sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and/or heating, sealing the periphery of the liquid crystal cell.
The liquid crystal cell with its periphery sealed is cut into panel units, and then the pressure is reduced in a vacuum chamber. The liquid crystal injection port is immersed in liquid crystal, and the liquid crystal is then injected into the liquid crystal cell by leaking the chamber.
The degree of reduced pressure inside the liquid crystal cell is usually 1×10 ⁻² Pa or more, preferably 1×10 ⁻³ or more, and usually 1×10 ⁻⁷ Pa or less, preferably 1×10 ⁻⁶ Pa or less, for example, 1×10 ⁻² to 1×10 ⁻⁷ Pa, 1×10 ⁻² to 1×10 ⁻⁶ Pa, 1×10 ⁻³ to 1×10 ⁻⁷ , or 1×10 ⁻³ to 1×10 ⁻⁶ .
It is preferable to heat the liquid crystal cell during the reduced pressure. When heating, the heating temperature is usually 30°C or higher, preferably 50°C or higher, and usually 100°C or lower, preferably 90°C or lower, for example, 30 to 100°C, 30 to 90°C, 50 to 100°C, or 50 to 90°C.

The heating and holding time under reduced pressure is usually in the range of 10 minutes to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal injection port of the liquid crystal cell into which the liquid crystal has been injected is sealed by curing a UV curable resin, thereby completing the liquid crystal display device (panel).
The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal, such as an aromatic, aliphatic, or polycyclic compound, such as a lyotropic or thermotropic liquid crystal. Known thermotropic liquid crystals include, for example, nematic, smectic, and cholesteric liquid crystals, and any of these may be used.

[4-2] Organic EL Display Device An organic EL display device having the color filter of the present invention can be produced by, for example, laminating an organic light-emitting body 500 on a blue color filter having pixels 20 formed from the colored resin composition of the present invention on a transparent supporting substrate 10 via an organic protective layer 30 and an inorganic oxide film 40, as shown in FIG. 1, thereby producing a multicolor organic EL element.

Examples of methods for laminating the organic light-emitting element 500 include a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter; and a method of bonding an organic light-emitting element 500 formed on a separate substrate onto the inorganic oxide film 40.
The organic EL element 100 thus fabricated can be applied to both passive-drive organic EL display devices and active-drive organic EL display devices.

Next, the present invention will be explained in more detail using examples and comparative examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention.

<Phthalocyanine dye A>
Phthalocyanine dye A having the following chemical structure, synthesized based on Example 30 of JP-A-05-345861, was used.

<Xanthene dye A>

Under a nitrogen atmosphere, N-acetamidophenol (13.0 g, 86 mmol) and 1,4-dibromobutane (30.6 mL, 258 mmol) were dissolved in acetone (200 mL), and potassium carbonate (23.8 g, 172 mmol) was added. The mixture was stirred under reflux for 16 hours. The reaction mixture was cooled to room temperature, the potassium carbonate was filtered off, and hexane (200 mL) was added. The resulting solid was collected by filtration and dried to obtain compound 1 (26.2 g).

Under a nitrogen atmosphere, compound 2 (4.59 g, 8 mmol) synthesized using the method described in JP 2013-253168 A and compound 1 (8.0 g, 28 mmol) were dissolved in N,N'-dimethylformamide (50 mL). Potassium carbonate (3.3 g, 24 mmol) was added and the mixture was stirred at 80°C for 16 hours. After cooling to room temperature, the reaction solution was added to water (100 mL). The resulting solid was filtered and purified by silica gel column chromatography (chloroform/methanol = 100/0 to 100/10 (volume ratio)). After filtering, the solid was vacuum dried at 10 mmHg and 70°C for 24 hours to obtain xanthene dye A (6.5 g, yield 65%).

<Xanthene dye B>

Xanthene dye B was synthesized using the method described in JP 2020-23660 A.

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

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

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

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

<Dispersion resin A>
A separable flask equipped with a condenser was prepared as a reaction vessel, and 400 parts by mass of propylene glycol monomethyl ether acetate was charged. After replacing the atmosphere with nitrogen, the reaction vessel was heated in an oil bath with stirring to a temperature of 90°C.

Meanwhile, the monomer tank was charged with 30 parts by weight of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by weight of methacrylic acid, 110 parts by weight of cyclohexyl methacrylate, 5.2 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate. The chain transfer agent tank was charged with 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate. Once the temperature of the reaction tank stabilized at 90°C, dropwise addition from the monomer tank and chain transfer agent tank began, initiating polymerization. The temperature was maintained at 90°C while the dropwise addition was carried out over 135 minutes. 60 minutes after the end of the dropwise addition, the temperature was raised 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 5/95 (v/v) oxygen/nitrogen mixed gas was initiated. 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 a dispersion resin A was obtained which had a weight average molecular weight Mw of 9000 in terms of polystyrene measured by GPC and an acid value of 101 mgKOH/g.

<Alkali-soluble resin A>
145 parts by weight of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen and heated to 120 ° C. 10 parts by weight of styrene, 90 parts by weight of glycidyl methacrylate, and 10 parts by weight of a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and stirring was continued for another 2 hours at 120 ° C. Next, the atmosphere in the reaction vessel was changed to air replacement, and 50 parts by weight of acrylic acid, 0.7 parts by weight of trisdimethylaminomethylphenol, and 0.12 parts by weight of hydroquinone were added, and the reaction was continued for 6 hours at 120 ° C. Thereafter, 13 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added, and the reaction was continued for 3.5 hours at 120 ° C. The weight average molecular weight Mw of the alkali-soluble resin A thus obtained, measured by GPC in terms of polystyrene, was 9000, and the acid value was 25 mg KOH / g.

<Alkali-soluble resin B>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while purging with nitrogen and heated to 120 ° C. 20 parts by mass of styrene, 57 parts by mass of glycidyl methacrylate, and 82 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and stirring was continued for another 2 hours at 120 ° C. Next, the atmosphere in the reaction vessel was replaced with air, and 27 parts by mass of acrylic acid, 0.7 parts by mass of trisdimethylaminomethylphenol, and 0.12 parts by mass of hydroquinone were added, and the reaction was continued for 6 hours at 120 ° C. Thereafter, 52 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was continued for 3.5 hours at 120 ° C. The weight average molecular weight (Mw) of the alkali-soluble resin B thus obtained, measured by GPC in terms of polystyrene, was 8000, and the acid value was 80 mg KOH / g.

<Preparation of Green Dye Dispersion A>
As shown in Table 1, 9.9 parts by mass of phthalocyanine dye A, 0.1 part by mass (in terms of solids content) of dispersant A, 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant A), 18.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were charged into a stainless steel container, and a dispersion treatment was carried out for 6 hours using a paint shaker. After completion of dispersion, the beads and the dispersion were separated using a filter, thereby preparing green dye dispersion A.

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

<Preparation of Yellow Pigment Dispersion A>
As shown in Table 1, 11.4 parts by mass of C.I. Pigment Yellow 138, 2.9 parts by mass of dispersant A in terms of solid content, 5.7 parts by mass of dispersion resin A in terms of solid content, 76.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant A and the solvent derived from dispersion resin A), 4.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and subjected to a dispersion treatment for 6 hours using a paint shaker. After completion of dispersion, the beads and the dispersion were separated using a filter to prepare yellow pigment dispersion A.

<Preparation of Blue Pigment Dispersion A>
As shown in Table 2, 12.4 parts by mass of C.I. Pigment Blue 15:6, 3.5 parts by mass of dispersant B (solids equivalent), 4.1 parts by mass of dispersion resin A (solids equivalent), 56.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant B and the solvent derived from dispersion resin A), 24.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and subjected to a dispersion treatment for 6 hours using a paint shaker. After completion of dispersion, the beads and dispersion liquid were separated using a filter to prepare blue pigment dispersion liquid A.

<Preparation of Purple Dye Dispersion A>
As shown in Table 2, 11.5 parts by mass of xanthene dye A, 4.6 parts by mass of dispersant B (solids equivalent), 3.9 parts by mass of dispersion resin A (solids equivalent), 76.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant B and the solvent derived from dispersion resin A), 4.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads with a diameter of 0.5 mm were charged into a stainless steel container, and dispersion treatment was carried out for 6 hours using a paint shaker. After dispersion was completed, the beads and dispersion liquid were separated using a filter to prepare purple dye dispersion liquid A.

<Preparation of Red Dye Dispersion A>
As shown in Table 3, 9.7 parts by mass of C.I. Pigment Red 177, 2.4 parts by mass of xanthene dye B, 3.1 parts by mass of dispersant B in solid content equivalent, 4.8 parts by mass of dispersion resin A in solid content equivalent, 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (including the solvent derived from dispersant B and the solvent derived from dispersion resin A), 8.0 parts by mass of propylene glycol monomethyl ether, and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and subjected to a dispersion treatment for 6 hours using a paint shaker. After completion of dispersion, the beads and the dispersion were separated using a filter to prepare red dye dispersion A.

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

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

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

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

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

<Chain Transfer Agent A>
Pentaerythritol tetra(3-mercaptopropionate) (manufactured by Yodo Chemical Co., Ltd.)

<Surfactant A>
Megafac F-554 (DIC)

<Preparation of Colored Resin Composition>
The components shown in Tables 4, 5, and 6 were mixed in the solid content ratios shown to prepare colored resin compositions. Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used so that the total solid content of the colored resin composition was 18.0% by mass. The PGMEA/PGME mixing ratio (mass ratio) in the obtained colored resin composition was 90/10.

<Measurement of color characteristics>
The colored resin composition was applied by spin coating to a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC), dried under reduced pressure, and then pre-baked on a hot plate at 90°C for 90 seconds. Next, a full-surface exposure treatment was performed using a 2 kW high-pressure mercury lamp with an exposure dose of 40 mJ/ ^cm2 and an illuminance of 30 mW/ ^cm2 . Thereafter, a development treatment was performed using a 0.04 mass% potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Next, a spray water rinse treatment was performed for 10 seconds at a water pressure of 1 kg/ ^cm2 . Then, a thermal curing treatment was performed in a clean oven at 230°C for 20 minutes to prepare a colored substrate.

The transmission spectra of the resulting green-colored substrates of Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a Hitachi U-3310 spectrophotometer, and the luminance was calculated when the chromaticity was sy = 0.578 with Illuminant C. The results are shown in Table 4.

Similarly, the luminance was calculated for the blue-colored substrates obtained in Example 3 and Comparative Example 3 when the chromaticity was sy = 0.101 under Illuminant C. The results are shown in Table 5.

Similarly, the luminance was calculated for the red-colored substrates obtained in Example 4 and Comparative Example 4 when the chromaticity was sx = 0.686 under Illuminant C. The results are shown in Table 6.

<Evaluation of pattern formability>
The colored resin composition was applied by spin coating onto a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC Inc.). The rotation speed was adjusted so that the chromaticity sy after heat curing treatment was 0.578 in Examples 1 and 2 and Comparative Examples 1 and 2, the chromaticity sy after heat curing treatment was 0.101 in Example 3 and Comparative Example 3, and the chromaticity sx after heat curing treatment was 0.686 in Example 4 and Comparative Example 4.
Each coating film was prebaked at 70°C for 90 seconds. Next, an exposure treatment was performed using a 2kW high-pressure mercury lamp with an exposure dose of 40 mJ/ ^cm2 and an illuminance of 30 mW/ ^cm2 , through an exposure mask having a circular covering portion with a diameter of 30 μm. Thereafter, a development treatment was performed using a 0.04 mass% potassium hydroxide aqueous solution at a developer temperature of 23°C for 60 seconds. Next, a spray water rinse treatment was performed at a water pressure of 1 kg/ ^cm2 for 10 seconds. Thereafter, a thermal curing treatment was performed at 230°C for 20 minutes to produce a patterned substrate A. For the resulting patterned substrate A, the diameter (μm) of the patterned hole portion was measured using an optical microscope (hole diameter A).

Next, pattern substrate B was produced under the same conditions as in the above process for pattern substrate A, except that the pre-baking temperature was changed from 70°C to 90°C. For the resulting pattern substrate B, the diameter (μm) of the pattern holes was measured using an optical microscope (hole diameter B).

The effect of the pre-bake temperature on the hole diameter was calculated from hole diameter A and hole diameter B, and this was used as an index of temperature dependency. The results of the pre-bake temperature dependency of hole diameter (= |(Hole diameter A - Hole diameter B) [μm]/(90-70) [°C]|) are shown in Tables 4, 5, and 6. The smaller the pre-bake temperature dependency of hole diameter, the smaller the effect of changes in pre-bake temperature on sensitivity, which is preferable because it allows for precise linewidth adjustment.

As is clear from Table 4, brightness is higher when phthalocyanine dye (1) is used as in Comparative Example 2 compared to the colored resin composition containing C.I. Pigment Green 58 (pigment) in Comparative Example 1. However, the use of phthalocyanine dye (1) increases the dependency of hole diameter on pre-bake temperature.

From Comparative Examples 1 and 2, it can be seen that the use of a dye as a colorant increases the dependency of the hole diameter on the pre-bake temperature.
Generally, regardless of the type of colorant, a large amount of residual solvent is present in a low temperature region such as a pre-bake temperature of 70°C, which increases the thickness of the coating film and increases the distance between polymerizable groups, resulting in a decrease in sensitivity, and it is thought that sufficient curing cannot be achieved, making the hole diameter large.

Comparative Example 1, in particular, contains a pigment without a dye, and the pigment has low affinity for the developer, which inhibits penetration of the developer into the pigment-containing coating, preventing excessive development even in low-temperature regions where curing is insufficient. This means that the hole diameter is less likely to change with changes in pre-bake temperature, and the dependency on pre-bake temperature is small, so it is believed that no issues with pre-bake temperature dependency have arisen.

On the other hand, since Comparative Example 2 contains a dye, it has a high affinity for the developer, which is thought to promote dissolution of the coating film in the developer. Furthermore, because dyes have a larger specific surface area than pigments, it is thought that radical deactivation of the photopolymerization initiator is more likely to occur on the colorant surface. Due to these factors, in Comparative Example 2, at low pre-bake temperatures such as 70°C, not only is the dissolution of the coating film in the developer promoted, but radical deactivation of the photopolymerization initiator is also promoted, resulting in larger hole diameters, which is thought to increase the dependency of hole diameter on pre-bake temperature.

In contrast, Examples 1 and 2 maintain high brightness while exhibiting small dependency of the hole diameter on the pre-bake temperature.
In Examples 1 and 2, the carbazole-based photopolymerization initiator B in Comparative Example 2 was replaced with photopolymerization initiator (d1) represented by formula (I) above. Photopolymerization initiator (d1) has a (keto)oxime ester group bonded to a less reactive indole ring, and therefore decomposes and reacts more slowly and continues to generate radicals intermittently than photopolymerization initiator B, which has a more reactive carbazole ring. This makes radical deactivation less likely to occur even in a low-temperature range where there is a large amount of residual solvent, such as a prebake temperature of 70°C, which is thought to be why the curability of the coating film improved and the dependency of the hole diameter on the prebake temperature was reduced.

Furthermore, from the comparison between Example 3 and Comparative Example 3 and the comparison between Example 4 and Comparative Example 4, it was found that, similar to the comparison between Example 1 and Comparative Example 2, even when using a xanthene dye (10) having a skeleton different from that of the phthalocyanine dye (1), the use of the photopolymerization initiator (d1) represented by the above formula (I) can achieve an improvement in the pre-bake temperature dependence of the hole diameter.

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

REFERENCE SIGNS LIST 10 transparent support substrate 20 pixel 30 organic protective layer 40 inorganic oxide film 50 transparent anode 51 hole injection layer 52 hole transport layer 53 light-emitting layer 54 electron injection layer 55 cathode 100 organic EL element 500 organic light-emitting body

Claims (7)

A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator,
The colorant (A) contains a phthalocyanine dye having a chemical structure represented by the following general formula (1):
The colored resin composition, wherein the (D) photopolymerization initiator contains a photopolymerization initiator (d1) represented by the following general formula (I):
(In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).)
(In formula (2), X represents a divalent linking group. The benzene ring in formula (2) may have any substituent. * represents a bond.)
(In formula (I), R ^d1 represents an alkyl group having 7 or less carbon atoms which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents an aromatic ring group which may have a substituent. 2. The colored resin composition according to claim 1, wherein in said formula (1), six or more of A ¹ to A ¹⁶ represent fluorine atoms. 3. The colored resin composition according to claim 1 , wherein in the photopolymerization initiator (d1), R ^d3 is a benzene ring having one free valence and which may have a substituent. The colored resin composition according to any one of claims 1 to 3 , wherein the content of the colorant (A) is 15 mass % or more of the total solid content. The colored resin composition according to any one of claims 1 to 4 , wherein the content of the photopolymerization initiator (d1) is 1.0 mass% or more of the total solid content. A color filter having pixels formed using the colored resin composition according to any one of claims 1 to 5 . An image display device comprising the color filter according to claim 6 .