WO2024075837A1

WO2024075837A1 - Colorant-containing liquid, colored resin composition, color filter, image display device, and method for producing colored resin composition

Info

Publication number: WO2024075837A1
Application number: PCT/JP2023/036548
Authority: WO
Inventors: 直也大村; 宏明石井; 大揮田嶋; 直人前田; 宏司砂留; 幸治福岡; 智之明治; 真彦吉住
Original assignee: 三菱ケミカル株式会社
Priority date: 2022-10-06
Filing date: 2023-10-06
Publication date: 2024-04-11

Abstract

Provided is a colored resin composition in which decreases in light exposure sensitivity are small even when the composition is stored over time after the preparation thereof. The colored resin composition contains (A) a coloring agent, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound with a specific structure and/or a benzoquinone compound. The coloring agent (A) contains a phthalocyanine compound having a specific structure.

Description

Colorant-containing liquid, colored resin composition, color filter, image display device, and method for producing colored resin composition

The present invention relates to a colorant-containing liquid, a colored resin composition, a color filter, an image display device, and a method for producing a colored resin composition.
This application claims priority based on Japanese Patent Application No. 2022-161334 filed in Japan on October 6, 2022, and Japanese Patent Application No. 2022-161335 filed in Japan on October 6, 2022, the contents of which are incorporated herein by reference.

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

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 material that determines 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 investigated (see, for example, Patent Document 1), and the use of xanthene dyes for blue pixel applications has been investigated (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 a satisfactory level of both sensitivity and transparency and brightness of the cured product.

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

The inventors have conducted research and found that in colored resin compositions containing dyes such as those described in Patent Documents 1 and 2, the exposure sensitivity of the colored resin composition is significantly reduced by storage over time after preparation of the colored resin composition, making pattern formation difficult. This has revealed the problem that high-definition color filters that are compatible with 4K and 8K resolutions, which require precise line width adjustment, cannot be stably manufactured.

The present invention aims to provide a colorant-containing liquid that can suppress the decrease in the exposure sensitivity of a colored resin composition even when stored over time after the preparation of the colored resin composition, and a colored resin composition that exhibits little decrease in exposure sensitivity even when stored over time after the preparation of the composition.

As a result of intensive research, the present inventors have found that the above problems can be solved by using a specific polymerization inhibitor in a colored resin composition containing a specific dye, and have arrived at the present invention.
That is, the present invention has the following configuration.

[1] A colorant-containing liquid containing (A) a colorant, (B) a solvent, and a compound represented by the following general formula (3) and/or a benzoquinone-based compound,
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1):
a total content of a compound represented by the following general formula (3) and a benzoquinone-based compound is 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the phthalocyanine compound:

(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 fluorine atom or 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 (3), R ^a , R ^b , R ^c , R ^d , and R ^f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ^e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)
[2] The colorant-containing liquid according to [1], wherein the content of the phthalocyanine compound is 50% by mass or more and 99.5% by mass or less based on the total solid content of the colorant-containing liquid.
[3] (E) The colorant-containing liquid according to [1], further containing a dispersant.
[4] The colorant-containing liquid according to [3], wherein the content ratio of the (A) colorant to the (E) dispersant ((A) colorant/(E) dispersant) on a mass basis is 10 or more.
[5] A colored resin composition comprising the colorant-containing liquid of [1], (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
[6] The colored resin composition according to [5], wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 30 parts by mass or less per 100 parts by mass of the (D) photopolymerization initiator.
[7] The colored resin composition according to [5], wherein the (A) colorant contains another colorant in addition to the phthalocyanine compound.
[8] A color filter having pixels formed using the colored resin composition according to [5].
[9] An image display device having the color filter of [8].
[10] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound represented by the following general formula (3) and/or a benzoquinone-based compound,
The colored resin composition, wherein the colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (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 fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).)

(In formula (3), R ^a , R ^b , R ^c , R ^d , and R ^f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ^e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)
[11] The colored resin composition according to [10], wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.001 mass% or more in the total solid content of the colored resin composition.
[12] The colored resin composition according to [10], wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.02 mass% or more in the total solid content of the colored resin composition.
[13] The colored resin composition according to [10], wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 0.80 mass% or less in the total solid content of the colored resin composition.
[14] The colored resin composition according to [10], wherein the content of the phthalocyanine compound is 5% by mass or more and 80% by mass or less in the total solid content of the colored resin composition.
[15] The colored resin composition according to [10], wherein the total content of the compound represented by the formula (3) and the benzoquinone-based compound is 20 parts by mass or less per 100 parts by mass of the (D) photopolymerization initiator.
[16] The colored resin composition according to [10], wherein the (A) colorant contains another colorant in addition to the phthalocyanine compound.
[17] A color filter having pixels formed using the colored resin composition according to any one of [10] to [16].
[18] An image display device having the color filter according to [17].
[19] A method for producing a colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound represented by the following general formula (3) and/or a benzoquinone-based compound,
The colorant (A) is a phthalocyanine compound having a chemical structure represented by the following general formula (1):
In the production of a colored resin composition, the phthalocyanine compound is mixed with a compound represented by the following general formula (3) and/or a benzoquinone-based compound before mixing the phthalocyanine compound with the (D) photopolymerization initiator:

(In formula (3), R ^a , R ^b , R ^c , R ^d , and R ^f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ^e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)
[20] The method for producing a colored resin composition according to [19], wherein the total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.001 mass% or more in the total solid content of the colored resin composition.
[21] The method for producing a colored resin composition according to [19], wherein the total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.02 mass% or more in the total solid content of the colored resin composition.
[22] The method for producing a colored resin composition according to [19], wherein the total amount of the compound represented by the formula (3) and the benzoquinone-based compound is 0.80 mass% or less in the total solid content of the colored resin composition.

According to the present invention, it is possible to provide a colorant-containing liquid capable of suppressing a decrease in the exposure sensitivity of a colored resin composition even during storage over time after the preparation of the colored resin composition.
According to the present invention, it is possible to provide a colored resin composition which shows little decrease in exposure sensitivity even during storage over time after the composition is prepared.

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 "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 other than the solvent in the colorant-containing liquid or colored resin composition. 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 is a value expressed as the mass of KOH equivalent to the amount of base per 1 g of solid content.
In the present invention, the acid value means an acid value calculated based on the effective solid content, unless otherwise specified, and is calculated by neutralization titration.
In the present invention, "C.I." means Color Index.
In the present invention, "(meth)acrylic" means "either one or both of acrylic and methacrylic".
In the present invention, the numerical range expressed using "to" means a range including the numerical values before and after "to" as the lower and upper limits.

[1] Colorant-Containing Liquid The colorant-containing liquid according to the present invention contains, as essential components, (A) a colorant, (B) a solvent, and a compound represented by formula (3) and/or a benzoquinone-based compound, and may further contain other additives, etc., other than the above components, as necessary.

[1-1] (A) Colorant The colorant-containing liquid of the present invention contains (A) a colorant. (A) The colorant is a component that colors the colorant-containing liquid. By including (A) the colorant, it is possible to obtain the desired light absorbency.

The colorant (A) in the colorant-containing liquid of the present invention contains a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter, may be referred to as "phthalocyanine compound (1)"). By containing phthalocyanine compound (1), the transmittance is improved, and a colored resin composition with high brightness can be obtained.

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 fluorine atom or a group represented by the following general formula (2).

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

( ^A1 to ^A16 )
In formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that at least one of A ¹ to A ¹⁶ represents a fluorine atom, or a group represented by the following general formula (2). From the viewpoint of heat resistance and solubility, it is preferred that at least one of A ¹ to A ¹⁶ represents a fluorine atom, and at least one of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

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.

At least one of A ¹ to A ¹⁶ is preferably a fluorine atom, more preferably 6 or more, even more preferably 7 or more, and particularly preferably 8 or more. Also, it is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. By making it equal to or more than the lower limit, the stability of the phthalocyanine compound (1) tends to be improved, and by making it equal to or less than the upper limit, the affinity with the dispersant and the 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, the number of substituents representing fluorine atoms among A ¹ to A ¹⁶ is 1 to 15, preferably 6 to 12, and more preferably 7 to 10.

(X)
X in formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, and 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). From the viewpoint of stability during firing of the phthalocyanine compound (1), 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 an arbitrary substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, an alkyl group (-R ^A group), an alkoxy group (-OR ^A group (wherein R ^A represents an alkyl group)), an alkoxycarbonyl group (-COOR ^A group (wherein R ^A represents an alkyl group)), an aryl group (-R ^B group), an aryloxy group (-OR ^B group (wherein R ^B represents an aryl group)), and an aryloxycarbonyl group (-COOR ^B group (wherein R ^B represents an aryl group)). From the viewpoints of development solubility and brightness, an alkoxycarbonyl group is preferred.

The alkyl groups contained in these groups may be linear, branched, or cyclic, but are 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 it equal to or more than the lower limit, aggregation tends to be suppressed, and foreign matter tends to be suppressed. In addition, by making it 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, and even more 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 preferable, and an ethyl group is more preferable.

The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The number of carbon atoms of 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 it equal to or more than the lower limit, there is a tendency to suppress aggregation due to steric repulsion. In addition, by making it equal to or less than the upper limit, there is a tendency to improve solvent affinity and stability over time.
The above upper and lower limits can be combined in any combination. For example, the aryl group preferably has 4 to 12 carbon atoms, more preferably 4 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene ring, each of which has one free valence.
The aromatic heterocycle in the aromatic heterocyclic group may be a monocycle 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, a benzofuran ring, a 2-benzofuran ring, a benzothiophene ring, a 2-benzothiophene ring, a 1H-pyrrolidine ring, an indole ring, an isoindole ring, an indolizine ring, a 2H-1-benzopyran ring, a 1H-2-benzopyran ring, a quinoline ring, an isoquinoline ring, a 4H-quinolizine ring, a benzimidazole ring, a 1H-indazole ring, a quinoxaline ring, a quinazoline ring, a cinnoline ring, a phthalazine ring, a 1,8-naphthyridine ring, a purine ring, and a pteridine ring, all of which have one free valence.

When the benzene ring in formula (2) has any substituent, the number of substitutions is not particularly limited. 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 per benzene ring is 1.
When the benzene ring in formula (2) has an arbitrary substituent, the substitution position thereof may be the o-position, the m-position, or the p-position. From the viewpoints of promoting π-π stacking between the phthalocyanine compound (1) molecules, improving heat resistance, and suppressing a decrease in luminance due to decomposition of the phthalocyanine compound (1), the p-position is preferred.

From the viewpoint of solubility in organic solvents and brightness, in formula (1), it is preferred that one or more of A ¹ to A ¹⁶ are groups represented by formula (2), one or more of A ¹ to A ⁴ are groups represented by formula (2), one or more of A ⁵ to A ⁸ are groups represented by formula (2), one or more of A ⁹ to A ¹² are groups represented by formula (2), and one or more of A ¹³ to A ¹⁶ are groups represented by formula (2); it is more preferred that two or more of A ¹ to A ⁴ are groups represented by formula (2), two or more of A ⁵ to A ⁸ are groups represented by formula (2), two or more of A ⁹ to A ¹² are groups represented by formula (2), and two or more of A ¹³ to A ¹⁶ are groups represented by formula (2).

From the viewpoint of stability of the phthalocyanine compound, it is preferable that in the formula (1), one or more of A ¹ to A ⁴ are fluorine atoms, one or more of A ⁵ to A ⁸ are fluorine atoms, one or more of A ⁹ to A ¹² are fluorine atoms, and one or more of A ¹³ to A ¹⁶ are fluorine atoms; it is more preferable that two or more of A ¹ to A ⁴ are fluorine atoms, two or more of A ⁵ to A ⁸ are fluorine atoms, two or more of A ⁹ to A ¹² are fluorine atoms, and two or more of A ¹³ to A ¹⁶ are fluorine atoms.

From the viewpoints of the maximum transmission wavelength and transmittance of the phthalocyanine compound (1), the affinity with the dispersant and solvent in the colorant-containing liquid, the uniformity of crystallization of the phthalocyanine compound during firing of the color filter, and the color tone required for the color filter, it is particularly preferable that A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ , and A ¹⁵ are groups represented by formula (2) and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ , and A ¹⁶ are fluorine atoms.

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

In the above formula, Et stands for ethyl.

The method for producing the phthalocyanine compound (1) can be a known method, for example, the method described in JP-A-05-345861.

The (A) colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of other colorants include dyes and pigments of the phthalocyanine compound (1). 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, for example, 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, 15 7, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and a 1:1 complex of azobarbituric acid and nickel represented by the following formula (i), or a compound obtained by inserting another compound into its tautomer (hereinafter, sometimes referred to as "nickel azo complex represented by formula (i)").

Furthermore, examples of the other compounds include compounds represented by the following formula (ii):

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

On the other hand, 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.

Among these, from the viewpoint of heat resistance and structural stability, phthalocyanine pigments having a central metal are preferred, and blue copper phthalocyanine pigments are particularly preferred. Preferred examples of the copper phthalocyanine pigment 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.
Among these, from the viewpoint of heat resistance, purple dioxazine pigments are preferred, and examples of the dioxazine pigment include C.I. Pigment Violet 19 and 23, and C.I. Pigment Violet 23 is even more preferred.

The average primary particle size of the pigment is preferably 0.2 μm or less, more preferably 0.1 μm or less, and even more preferably 0.04 μm or less. When atomizing the pigment, a method such as the above-mentioned solvent salt milling is preferably used.

The content ratio of the phthalocyanine compound (1) in the colorant-containing liquid of the present invention is preferably 50% by mass or more, more preferably 80% by mass or more, based on the total solid content of the colorant-containing liquid. Also, it is preferably 99.5% by mass or less, more preferably 99% by mass or less. By making it equal to or less than the upper limit, the stability of the colorant-containing liquid tends to be improved. By making it equal to or more than the lower limit, the coloring power tends to be improved. The upper and lower limits can be combined arbitrarily.
For example, the content of the phthalocyanine compound (1) in the total solid content of the colorant-containing liquid is preferably 50 to 99.5% by mass, and more preferably 80 to 99% by mass.

The content of the colorant (A) in the total solid content of the colorant-containing liquid is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, and is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less. If the content of the colorant (A) is equal to or more than the lower limit, the coloring power tends to be improved, and if it is equal to or less than the upper limit, the stability of the colorant-containing liquid tends to be improved.
The upper and lower limits can be combined in any combination. For example, the content is preferably 40 to 99.9% by mass, more preferably 50 to 99.5% by mass, and even more preferably 60 to 99% by mass.

[1-2] (B) Solvent The (B) solvent has the function of dissolving or dispersing the (A) colorant, the compound represented by the formula (3) and/or the benzoquinone-based compound, and other components in the color-containing liquid of the present invention, and adjusting the viscosity.
The solvent (B) may be any solvent capable of dissolving or dispersing each of the components.

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 of the nitrile include acetonitrile and benzonitrile.

Commercially available solvents that fall under the above category include, for example, mineral spirits, Valsol #2, Apco #18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2, Solvesso #150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve, Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, and Diglyme (all trade names). These solvents may be used alone or in combination of two or more.

When forming pixels of a color filter by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 200°C (under a pressure condition of 1013.25 [hPa]. The same applies to all boiling points below.) More preferably, the solvent has a boiling point of 120 to 170°C.
Glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, and the like in the above-mentioned solvents, and the solubility of the components in the colorant-containing liquid 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. Among them, propylene glycol monomethyl ether is particularly preferred from the viewpoint of the solubility of the components in the colorant-containing liquid. Glycol monoalkyl ethers have high polarity, and if too much is added, the pigments tend to aggregate, and the viscosity of the colored resin composition obtained later tends to increase, decreasing the storage stability. Therefore, the proportion of glycol monoalkyl ethers in the (B) solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

In another embodiment, a solvent having a boiling point of 150° C. or higher can be used in combination.
By using a solvent having a boiling point of 150 ° C. or more in combination, the colored resin composition is less likely to dry, but there is an effect of making it difficult for the interrelationship between the components in the colorant-containing liquid to be destroyed due to rapid drying. When using a solvent having a boiling point of 150 ° C. or more in combination, the content ratio of the solvent having a boiling point of 150 ° C. or more in the (B) solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it to the lower limit or more, for example, there is a tendency to easily avoid the coloring material components and the like precipitating and solidifying at the tip of the slit nozzle, causing foreign matter defects, and by setting it to the upper limit or less, there is a tendency to easily avoid the drying speed of the colored resin composition being slowed down, causing problems such as poor tact in the reduced pressure drying process and pin marks in the pre-bake.
The solvent having a boiling point of 150° C. or higher may be either a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately contain a solvent having a boiling point of 150° C. or higher.
Preferred examples of the solvent 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 the inkjet method, the solvent should have a boiling point of usually 130° C. or higher and 300° C. or lower, preferably 150° C. or higher and 280° C. or lower. By setting the boiling point to be equal to or higher than the lower limit, the uniformity of the resulting coating film tends to be good, and by setting the boiling point to be equal to or lower than the upper limit, the amount of residual solvent during baking tends to be reduced.
From the viewpoint of uniformity of the resulting coating film, the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, and more preferably 1 mmHg or less.

In color filter manufacturing using the inkjet method, the colorant-containing liquid (ink) emitted from the nozzle is very fine, at several to several tens of pL, so the solvent tends to evaporate and the ink tends to concentrate and dry up before landing around the nozzle opening or inside the pixel bank. In order to avoid this, it is preferable that the (B) solvent contains a solvent with a high boiling point, specifically, a solvent with a boiling point of 180°C or higher. It is more preferable to contain a solvent with a boiling point of 200°C or higher, and particularly preferable to contain a solvent with a boiling point of 220°C or higher. When a solvent with a boiling point of 180°C or higher is used in combination, the content of the solvent with a boiling point of 180°C or higher in the (B) solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting it to the above lower limit or more, the effect of preventing the evaporation of the solvent from the droplets tends to be fully exerted.

Examples of solvents having a boiling point of 180° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin, among the various solvents mentioned above.
In order to adjust the viscosity of the colorant-containing liquid or the colored resin composition or the solubility of the solid content, it is effective to partially contain a solvent having a boiling point lower than 180° C. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, for example, ethers, esters, and ketones are preferable. Among them, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferable.

On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. When alcohols are used in combination, the content of alcohols in the (B) solvent 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 (B) solvent in the colorant-containing liquid of the present invention is not particularly limited, but the upper limit is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. By setting the content below the upper limit, it tends to be easier to form a coating film. On the other hand, the lower limit of the solvent content is preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 75% by mass or more, taking into consideration the viscosity suitable for application. The above upper and lower limits can be combined arbitrarily. For example, the content of the solvent in the colored resin composition is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and even more preferably 75 to 90% by mass.

[1-3] Compound represented by formula (3) and benzoquinone-based compound The colorant-containing liquid of the present invention contains a compound represented by the following general formula (3) and/or a benzoquinone-based compound, and among these, it preferably contains a compound represented by the following general formula (3).

(In formula (3), R ^a , R ^b , R ^c , R ^d , and R ^f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R ^e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)

Phthalocyanine compound (1) has a fluorine atom with extremely high electronegativity or a group represented by formula (2) which is an electron-donating group, and therefore has high molecular polarity and is considered to have high affinity with compounds represented by formula (3) and benzoquinone-based compounds. Phthalocyanine compounds generally have high molecular planarity, and among them, phthalocyanine compound (1) has a fluorine atom with an extremely small atomic radius or a group represented by formula (2) which has high planarity, and therefore has small steric hindrance and is considered to have high affinity with compounds represented by formula (3) and benzoquinone-based compounds. Therefore, the colorant-containing liquid of the present invention contains a compound represented by formula (3) and/or a benzoquinone-based compound, and therefore, it is considered that phthalocyanine compound (1) and compounds represented by formula (3) and benzoquinone-based compounds are close to each other in the colorant-containing liquid. As a result, even when the colorant-containing liquid and the (D) photopolymerization initiator are mixed to prepare a colored resin composition, it is believed that it is possible to suppress a decrease in the polymerization ability and film hardening ability of the (D) photopolymerization initiator caused by the phthalocyanine compound (1) approaching the (D) photopolymerization initiator and the interaction between the phthalocyanine compound (1) and the (D) photopolymerization initiator.

Examples of the compound represented by formula (3) include hydroquinones such as methylhydroquinone (MHQ), phenols such as 4-methoxyphenol (MEHQ) and dibutylhydroxytoluene (BHT), and hindered phenols such as pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate].
An example of the benzoquinone compound is 1,4-benzoquinone.
Among the compounds represented by formula (3) and the benzoquinone-based compounds, from the viewpoint of affinity with the phthalocyanine compound (1), specifically, from the viewpoint of molecular polarity and steric hindrance of the molecule, methylhydroquinone (MHQ), 4-methoxyphenol (MEHQ), dibutylhydroxytoluene (BHT), and pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate] are preferred, and methylhydroquinone (MHQ) and 4-methoxyphenol (MEHQ) are particularly preferred.

The compound represented by formula (3) and the benzoquinone-based compound may be used alone or in combination of two or more.

The total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.80 mass% or less, more preferably 0.50 mass% or less, even more preferably 0.30 mass% or less, and particularly preferably 0.10 mass% or less, based on the total solid content of the colorant-containing liquid. Also, it is preferably 0.001 mass% or more, more preferably 0.005 mass% or more, even more preferably 0.008 mass% or more, and particularly preferably 0.01 mass% or more. By making it equal to or greater than the lower limit, there is a tendency that the interaction between the phthalocyanine compound (1) and the photopolymerization initiator can be suppressed. Also, by making it equal to or less than the upper limit, there is a tendency that a pattern with high curability and good linearity can be formed. The upper and lower limits can be combined in any manner. For example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.001 to 0.80% by mass, more preferably 0.005 to 0.50% by mass, even more preferably 0.008 to 0.10% by mass, and particularly preferably 0.01 to 0.10% by mass, based on the total solid content of the colorant-containing liquid.

The total content of the compound represented by formula (3) and the benzoquinone-based compound is 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the phthalocyanine compound (1). By making it equal to or more than the lower limit, the interaction between the phthalocyanine compound (1) and the photopolymerization initiator tends to be suppressed. Also, by making it equal to or less than the upper limit, a pattern with high curability and good linearity tends to be formed.
The total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.08 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the phthalocyanine compound (1). Also, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less. The above upper and lower limits can be arbitrarily combined. For example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.05 to 5 parts by mass, more preferably 0.08 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the phthalocyanine compound (1).

Here, "the total content of the compound represented by formula (3) and the benzoquinone-based compound" does not presume that both the compound represented by formula (3) and the benzoquinone-based compound are contained, but includes embodiments in which only one of the compound represented by formula (3) or the benzoquinone-based compound is contained.

[1-4] (E) Dispersant The colorant-containing liquid of the present invention may contain (E) a dispersant. When a pigment is contained as (A) the colorant, it is preferable that the colorant-containing liquid contains (E) a dispersant for the purpose of stably dispersing the pigment. Among dispersants, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time.
Examples of the polymer dispersant 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 the polymer dispersant include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemical Industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and polymer dispersants described in JP 2013-119568 A.

Among the polymer dispersants, from the viewpoints 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.
As the block copolymer having a functional group containing a nitrogen atom, 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 a side chain and a B block not having a quaternary ammonium base and/or an amino group is preferable.

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 viewpoints of dispersibility and storage stability, it is preferably a repeating unit represented by the following general formula (11).

In formula (11), ^R11 and ^R12 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and ^R11 and ^R12 may be bonded to each other to form a ring structure. ^R13 is a hydrogen atom or a methyl group. X is a divalent linking group.

The number of carbon atoms in the alkyl group, which may have a substituent, in formula (11) is not particularly limited, but is usually 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, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. The alkyl group may be either linear or branched. It may also include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

In formula (11), the number of carbon atoms of the aryl group, which may have a substituent, is not particularly limited, but is usually 6 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 8 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.

In formula (11), the number of carbon atoms in the aralkyl group, which may have a substituent, is not particularly limited, but is usually 7 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. Examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, with the phenylmethylene group, phenylethylene group, phenylpropylene group, and phenylbutylene group being preferred, and the phenylmethylene group and phenylethylene group being more preferred.

From the viewpoints of dispersibility, storage stability, electrical reliability, and developability, R ¹¹ and R ¹² are preferably each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

Examples of the substituent that the alkyl group, aralkyl group, or aryl group in formula (11) may have include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, and from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

In formula (11), the cyclic structure formed by bonding R ¹¹ and R ¹² to each other may be, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of these. The nitrogen-containing heterocycle is preferably one that does not have aromaticity, and more preferably a saturated ring. For example, the following nitrogen-containing heterocycle (VII) may be mentioned.

These ring structures may further have substituents.

In formula (11), 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 - group, and ^a -COOR - group (wherein ^R and ^R are single bonds, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), and ^a -COO-R - group is preferred.

The content of the repeating unit represented by formula (11) in the total 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 above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 90 mol%, 5 to 90 mol%, 10 to 70 mol%, 15 to 70 mol%, 20 to 50%, or 25 to 40 mol%. Within the above range, there is a tendency for both dispersion stability and high brightness to be achieved.

The block copolymer preferably has a repeating unit represented by the following general formula (12) from the viewpoint of increasing the compatibility of the dispersant with binder components such as the solvent and improving dispersion stability.

In formula (12), R ¹¹⁰ is an ethylene group or a propylene group, R ¹¹¹ is an alkyl group which may have a substituent, R ¹¹² is a hydrogen atom or a methyl group, and n is an integer of 1 to 20.

The number of carbon atoms of the alkyl group which may have a substituent in R ¹¹¹ of formula (12) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 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, and are preferably methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, and more preferably methyl, ethyl, propyl, and butyl groups. They may be either linear or branched. They may also include a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. Examples of the substituent include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, and from the viewpoint of ease of synthesis, unsubstituted groups are preferable.

In formula (12), n is preferably 1 or more, more preferably 2 or more, and is preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersibility in binder components such as solvents. The upper and lower limits above can be combined in any manner. For example, it may be 1 to 10, or 2 to 5.

The content of the repeating unit represented by formula (12) in all repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 1 to 30 mol%, 2 to 20 mol%, or 4 to 10 mol%. Within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability.

The block copolymer preferably has a repeating unit represented by the following general formula (13) from the viewpoint of increasing the compatibility of the dispersant with binder components such as the solvent and improving dispersion stability.

In formula (13), ^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 of the alkyl group which may have a substituent in R ⁸ of formula (13) is not particularly limited, but is usually 1 or more, preferably 1 or more, and more preferably 10 or less, and more preferably 6 or less. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl groups, with methyl, ethyl, propyl, butyl, pentyl, and hexyl being preferred, and methyl, ethyl, propyl, and butyl being more preferred. The alkyl group may be either linear or branched. It may also 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 formula (13) 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, of which a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, and a diethylphenyl group are preferred, and a phenyl group, a methylphenyl group, and an ethylphenyl group are more preferred.

The number of carbon atoms in the aralkyl group which may have a substituent in ^R8 of formula (13) 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 phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenylisopropylene group, with the phenylmethylene group, phenylethylene group, phenylpropylene group, and phenylbutylene group being preferred, and the phenylmethylene group and phenylethylene 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 phenylmethylene 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 (13) in the total repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more, even more preferably 50 mol% or more, and preferably 80 mol% or less, and more preferably 70 mol% or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 30 to 80 mol%, 40 to 80 mol%, or 50 to 70 mol%. Within the above range, it tends to be possible to achieve both dispersion stability and high brightness.

The block copolymer may have repeating units other than the repeating units represented by formula (11), the repeating units represented by formula (12), and the repeating units represented by formula (13). Examples of such repeating units include repeating units derived from monomers such as 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 improving dispersibility, it is preferable that the block copolymer has an A block having a repeating unit represented by formula (11) and a B block having no repeating unit represented by formula (11). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. It is more preferable that the B block has a repeating unit represented by formula (12) and a repeating unit represented by formula (13).

　Repeat units other than the repeat unit represented by formula (11) may be contained in the A block, and examples of such repeat units include the repeat units derived from the (meth)acrylic acid ester monomers described above. The content of repeat units other than the repeat unit represented by formula (11) in the A block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is particularly preferable that such repeat units are not contained in the A block.

　Repeat units other than the repeat units represented by formula (12) and the repeat units represented by formula (13) may be contained in the B block, and examples of such repeat units include repeat 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 repeat units other than the repeat units represented by formula (12) and the repeat units represented by formula (13) in the B block is preferably 0 to 50 mol %, more preferably 0 to 20 mol %, and it is particularly preferable that such repeat units are not contained in the B block.

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

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, most preferably 105 mgKOH/g or more, and preferably 150 mgKOH/g or less, more preferably 130 mgKOH/g or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 30 to 150 mgKOH/g, 50 to 150 mgKOH/g, 70 to 150 mgKOH/g, 90 to 130 mgKOH/g, 100 to 130 mgKOH/g, or 105 to 130 mgKOH/g. Here, the amine value refers to the amine value calculated based on 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 of the dispersant.

The molecular weight of the block copolymer is preferably in the range of 1000 to 30,000 in terms of polystyrene equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). If it is within this range, the dispersion stability will be good, and there is a tendency that the generation of dried foreign matter during application using the slit nozzle method will be less likely.

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

When the colorant-containing liquid of the present invention contains a dispersant (E), the content of the dispersant (E) 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 preferably 20% by mass or less, more preferably 15% 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 colorant-containing liquid. By setting the content to be equal to or greater than the lower limit, there is a tendency for dispersibility and storage stability to be improved, and by setting the content to be equal to or less than the upper limit, there is a tendency for electrical reliability and developability to be improved. The upper and lower limits can be combined in any combination. For example, it may be 0.001 to 20% by mass, 0.01 to 15% by mass, 0.1 to 10% by mass, or 1 to 5% by mass or more.

When the colorant-containing liquid of the present invention contains a dispersant (E), the content ratio of the colorant (A) to the dispersant (E) on a mass basis (colorant (A)/dispersant (E)) is preferably 10 or more, more preferably 25 or more, and even more preferably 50 or more. Also, it is preferably 200 or less, more preferably 150 or less, and even more preferably 100 or less. By setting it to the upper limit or less, the storage stability of the colorant-containing liquid tends to improve, and by setting it to the lower limit or more, the electrical reliability and developability tend to improve. The upper and lower limits can be combined in any combination. For example, it may be 10 to 200 to 100, 25 to 150, or 50 to 100.

When the colorant-containing liquid of the present invention contains a pigment and a dispersant (E), the content ratio of the dispersant (E) 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, even more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, relative to 100 parts by mass of the pigment, and is also preferably 70 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0.5 to 70 parts by mass, 5 to 70 parts by mass, 10 to 50 parts by mass, 15 to 40 parts by mass, or 20 to 30 parts by mass. By keeping it within the above range, it tends to be possible to obtain a colorable resin composition with excellent dispersion stability and high brightness.

When the colorant-containing liquid of the present invention contains a pigment, it may contain a pigment derivative or the like as a dispersing aid to improve the dispersibility and dispersion stability of the pigment. Examples of pigment derivatives include 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 pigment derivatives. Substituents of the pigment derivative include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, amide groups, etc., which are bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, etc., and preferably sulfonamide groups and their quaternary salts, and sulfonic acid groups, and more preferably sulfonic acid groups. These substituents may be substituted in multiple ways on one pigment skeleton, or a mixture of compounds with different numbers of substitutions may be used. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, sulfonic acid derivatives of diketopyrrolopyrrole pigments, and sulfonic acid derivatives of dioxazine pigments.

The colorant-containing liquid of the present invention may further contain, as necessary, the colorant (A), the solvent (B), the compound represented by formula (3), a benzoquinone-based compound, and other components. Examples of the other components include other blending components in the colored resin composition described below.
The content of other components relative to the total solid content of the colorant-containing liquid is preferably 5% by mass or less, more preferably 1% by mass or less, and may be 0% by mass.

[1-5] Method for Producing Colorant-Containing Liquid The colorant-containing liquid of the present invention is produced, for example, by mixing optional components such as (A) a colorant, (B) a solvent, a compound represented by formula (3), a benzoquinone-based compound, and (E) a dispersant as necessary, and subjecting the resulting mixed liquid to a dispersion treatment.

The dispersion treatment can be carried out using a known dispersion treatment device such as a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, etc. When the dispersion treatment is carried out using a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.
The dispersion treatment conditions are not particularly limited, but the temperature is, for example, in the range of 0° C. to 100° C., and preferably in the range of room temperature to 60° C. The dispersion time is appropriately adjusted since the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment device, etc.
After the dispersion treatment, if necessary, the resulting dispersion may be filtered using a filter or the like to separate the beads used in the dispersion treatment from the colorant-containing liquid.

When no dispersion treatment is performed, the colorant-containing liquid of the present invention is produced by mixing (A) the colorant, (B) the solvent, the compound represented by formula (3), the benzoquinone-based compound, and optional components as necessary.

[2] Colored resin composition (first embodiment)
One embodiment of the colored resin composition of the present invention contains the colorant-containing liquid of the present invention, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.

[2-1] (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.

Examples of the alkali-soluble resin (C) that can be used include 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. Preferred examples include the following resins (C-1) to (C-5) (hereinafter, each of which may be referred to as resins (C-1) to (C-5)).
(C-1): An alkali-soluble 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 by adding a polybasic acid anhydride to at least a portion of the hydroxyl groups produced by the addition reaction (hereinafter, sometimes referred to as "resin (C-1)").
(C-2) A linear alkali-soluble resin containing a carboxy group in the main chain (hereinafter, sometimes referred to as "resin (C-2)").
(C-3) A resin in which an epoxy-containing unsaturated compound is added to the carboxy group portion of the resin (C-2) (hereinafter, sometimes 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 carboxy group (hereinafter, may be referred to as "resin (C-5)").

Particularly preferred is resin (C-1).
Resins (C-2) to (C-5) may be any resins so long as they are dissolved in an alkaline developer and have a solubility sufficient to allow the intended development process to be carried out. For each of these resins, those described in JP 2009-025813 A can be used.

(C-1) A resin obtained by adding an unsaturated monobasic acid to at least a portion of the epoxy groups of 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 generated by the addition reaction. One of the preferred aspects of the resin (C-1) is "a resin obtained by adding an unsaturated monobasic acid to 10 to 100 mol % of the epoxy groups of 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 generated by the addition reaction."

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

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

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), the ring formed by combining R ⁹⁶ and R ⁹⁸ , or R ⁹⁵ and R ⁹⁷ , is preferably an aliphatic ring, which may be either saturated or unsaturated, and preferably has 5 to 6 carbon atoms.

The structure represented by 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 pixels formed using the colored resin composition tends to increase.

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

As the mono(meth)acrylate having the structure represented by formula (V), various known compounds can be used as long as they have the structure, but mono(meth)acrylates represented by 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 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 formula (VI), the content of the repeating unit derived from the mono(meth)acrylate represented by 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 particularly preferably 15 to 50 mol %.

Other radical polymerizable monomers other than the mono(meth)acrylate represented by formula (VI) are not particularly limited, but specific examples include vinyl aromatics such as styrene, α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, and the like. Hexyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthracenyl (meth)acrylate, anthraninonyl (meth)acrylate, piperonyl (meth)acrylate, salicyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, (meth)acrylic (meth)acrylic acid esters such as pyranyl acid, benzyl (meth)acrylate, phenethyl (meth)acrylate, cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, perfluoro-iso-propyl (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 (Meth)acrylic acid amides such as N,N-dipropylamide, (meth)acrylic acid N,N-di-iso-propylamide, 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 these other radical polymerizable monomers, styrene, benzyl (meth)acrylate, and monomaleimide are preferred from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition.
When the copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer contains any repeating unit derived from styrene, benzyl (meth)acrylate, or monomaleimide, the total content of the repeating units derived from styrene, the repeating units derived from benzyl (meth)acrylate, and the repeating units derived from monomaleimide in the repeating units derived from the other radically polymerizable monomer is preferably 1 to 70 mol %, more preferably 3 to 50 mol %.

The copolymerization reaction of the epoxy group-containing (meth)acrylate with other radical polymerizable monomers is carried out by a known solution polymerization method. The solvent used is not particularly limited as long as it is inactive to radical polymerization, and any commonly used organic solvent can be used.
Examples of the solvent used in the solution polymerization method include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, 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; methyl carbitol, ethyl carbitol, butyl carbitol, and the like. Examples of the solvent include diethylene glycol dialkyl ethers such as 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 in the solution polymerization method is usually 30 to 1,000 parts by mass, and preferably 50 to 800 parts by mass, per 100 parts by mass of the resulting copolymer. By keeping the amount of solvent used within the above range, it tends to be easier to control the molecular weight of the copolymer.

The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. Examples of organic peroxide catalysts include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Examples of radical polymerization initiators used in the copolymerization reaction include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3-isopropyl Examples of the peroxyalkylene oxide include hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, and 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane.
Examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbonamide.

Among these, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature.
The amount of the radical polymerization initiator used is usually 0.5 to 20 parts by mass, and preferably 1 to 10 parts by mass, based on 100 parts by mass of the total of the monomers used in the copolymerization reaction.

The copolymerization reaction may be carried out by dissolving the monomers and radical polymerization initiator used in the copolymerization reaction in a solvent and heating the mixture while stirring, or by adding the monomers to which the radical polymerization initiator has been added dropwise into a heated and stirred solvent, or by adding the radical polymerization initiator to a solvent and then dropping the monomers into the heated mixture. The reaction conditions can be set according to the target molecular weight.

In the present invention, the copolymer of an epoxy group-containing (meth)acrylate and another radical polymerizable monomer is preferably one that, among all repeating units of the copolymer, consists of 5 to 90 mol % of repeating units derived from the epoxy group-containing (meth)acrylate and 10 to 95 mol % of repeating units derived from the other radical polymerizable monomer; more preferably one that consists 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 radical polymerizable monomer; and particularly preferably one that consists 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 radical polymerizable monomer.

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

Resin (C-1) is made by reacting an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component) with the epoxy groups of a copolymer of an epoxy resin-containing (meth)acrylate and another radically polymerizable monomer.

Examples of unsaturated monobasic acids to be added to epoxy groups include (meth)acrylic acid; crotonic acid; o-, m-, and p-vinylbenzoic acid; and monocarboxylic acids such as (meth)acrylic acid substituted at the α-position with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. Of these, (meth)acrylic acid is preferred. These unsaturated monobasic acids may be used alone or in combination of two or more.

By adding an unsaturated monobasic acid to the epoxy group, it is possible to impart polymerizability to the resin (C-1).
The unsaturated monobasic acid is added to an amount of usually 10 to 100 mol %, preferably 30 to 100 mol %, and more preferably 50 to 100 mol %, based on 100 mol % of all epoxy groups possessed by the copolymer of the epoxy resin-containing (meth)acrylate and other radically polymerizable monomer.
By making the content equal to or greater than the above lower limit, the colored resin composition tends to have good stability over time.
As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Furthermore, as the polybasic acid anhydride to be added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known polybasic acid anhydrides can be used.
Examples of polybasic acid anhydrides include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; and anhydrides of tribasic or higher acids such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, and biphenyltetracarboxylic anhydride. Among them, tetrahydrophthalic anhydride and succinic anhydride are preferred. These polybasic acid anhydrides may be used alone or in combination of two or more.

By adding a polybasic acid anhydride to the hydroxyl group generated when an unsaturated monobasic acid is added to the epoxy group of the copolymer, alkali solubility can be imparted to the resin (C-1).
The polybasic acid anhydride is added in an amount of usually 10 to 100 mol %, preferably 20 to 90 mol %, and more preferably 30 to 80 mol %, assuming that the total hydroxyl groups generated by adding the unsaturated monobasic acid to the epoxy groups of the copolymer is 100 mol %. By making it equal to or less than the upper limit, the residual film ratio at the time of development tends to be good, and by making it equal to or more than the lower limit, the solubility tends to be sufficient.
As a method for adding a polybasic acid anhydride to a hydroxyl group generated by adding an unsaturated monobasic acid to an epoxy group of the copolymer, a known method can be adopted.

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

Examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group.
Examples of commercially available products include those sold 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" manufactured by Nagase ChemteX Corporation.

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

The weight average molecular weight (Mw) of the resin (C-1) measured by GPC in terms of polystyrene is not particularly limited, but is preferably 3000 or more, and more preferably 5000 or more. It is preferably 100,000 or less, and more preferably 50,000 or less. The upper and lower limits can be arbitrarily combined. For example, it may be 3000 to 100,000, or 5000 to 50,000. By making it equal to or more than the lower limit, the heat resistance and film strength tend to be good, and by making it equal to or less than the upper limit, the solubility in the developer tends to be good.
As a guide for the molecular weight distribution, the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) of the resin (C-1) is preferably from 2.0 to 5.0.

From the viewpoint of coating film curing properties upon exposure to ultraviolet light, (c1) an acrylic copolymer resin having an ethylenically unsaturated group in a side chain (hereinafter, sometimes referred to as (c1) acrylic copolymer resin) is preferred among the resins (C-4).
The partial structure containing a side chain having an ethylenically unsaturated group that the acrylic copolymer resin (c1) has is not particularly limited. From the viewpoint of achieving both coating film curability upon exposure to ultraviolet light and alkali solubility upon alkali development, it is preferable for the partial structure to 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), 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 means a monovalent or divalent group obtained by removing one or two OH groups from a polybasic acid. Examples of the polybasic acid include one or more selected from 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.
Among these, from the viewpoint of patterning characteristics, preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid, and more preferred are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

When the (c1) acrylic copolymer resin has a partial structure represented by formula (I), the content ratio of the partial structure represented by formula (I) contained in the (c1) acrylic copolymer resin 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 making it equal to or more than the lower limit, the coating film curability during exposure to ultraviolet light tends to improve, and by making it equal to or less than the upper limit, the alkali solubility during alkali development tends to improve. The upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I) in the (c1) acrylic copolymer resin 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 has a partial structure represented by formula (I'), the content ratio of the partial structure represented by formula (I') contained in the (c1) acrylic copolymer resin 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 making it equal to or more than the lower limit, the coating film curability during exposure to ultraviolet light tends to improve, and by making it equal to or less than the upper limit, the alkali solubility during alkali development tends to improve. The upper and lower limits can be combined arbitrarily. For example, the content of the partial structure represented by formula (I') in the (c1) acrylic copolymer resin 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 the acrylic copolymer resin contains a partial structure represented by formula (I), the other partial structures contained therein are not particularly limited, but from the viewpoint of alkaline solubility during alkaline development, it is also preferable that the resin has a partial structure represented by the following general formula (II), for example.

In 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.

( ^R4 )
In 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 R ⁴ 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 it to the lower limit or more, lipophilicity tends to be improved and solubility in solvents tends to be improved, and by setting it to the upper limit or less, hydrophilicity tends to be improved and alkali solubility tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkyl group is preferably 1 to 20, 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 carboxy group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The aromatic ring group in R ⁴ includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, and is preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. By making the number of carbon atoms equal to or more than the lower limit, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and by making the number of carbon atoms equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, even more preferably 6 to 20, and particularly preferably 6 to 18.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, 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.
In addition, the aromatic heterocycle in the aromatic heterocycle group may be a single ring or a condensed ring, and examples thereof include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.From the viewpoint of development, benzene ring group and naphthalene ring group are preferred, and benzene ring group 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 carboxy group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkenyl group in R ⁴ 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 making the number of carbon atoms equal to or more than the lower limit, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and by making the number of carbon atoms equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

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 the substituents that the alkenyl 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, and a carboxy group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

^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. From the viewpoints of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

When the (c1) acrylic copolymer resin has a partial structure represented by formula (II), the content ratio of the partial structure represented by formula (II) in the (c1) acrylic copolymer resin 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 also 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, there is a tendency for the alkali solubility to be improved, and by making it equal to or less than the upper limit, there is a tendency for the storage stability of the colored resin composition to be improved. For example, the content ratio of the partial structure represented by formula (II) in the (c1) acrylic copolymer resin is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, even more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

(c1) When the acrylic copolymer resin contains a partial structure represented by formula (I), it is preferable that the other partial structures contained therein contain a partial structure represented by the following general formula (III), from the viewpoint of suppressing a decrease in brightness by improving heat resistance.

In formula (III), ^R5 represents a hydrogen atom or a methyl group, and ^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 hydroxy group, a carboxy group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent.
t represents an integer of 0 to 5.

( ^R6 )
In 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 hydroxy group, a carboxy group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent.
The alkyl group in R ⁶ 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, 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 to be equal to or more than the lower limit, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and by setting the number of carbon atoms to be equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkyl group 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. Among these, 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 carboxy 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 R ⁶ 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 to be equal to or more than the lower limit, lipophilicity and solubility in a solvent tend to be improved, and by setting the number of carbon atoms to be equal to or less than the upper limit, hydrophilicity and alkali solubility tend to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkenyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

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. Among these, from the viewpoint of exposure sensitivity when exposed to ultraviolet light, vinyl groups and allyl groups are preferred, and vinyl groups are more preferred.

The alkynyl group in R ⁶ 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 to be equal to or more than the lower limit, lipophilicity and solubility in a solvent tend to be improved, and by setting the number of carbon atoms to be equal to or less than the upper limit, hydrophilicity and alkali solubility tend to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkynyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

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 the substituent that the alkynyl 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, and a carboxy group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group 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 (c1) acrylic copolymer resin, a fluorine atom is preferred.

The alkoxy group in R ⁶ 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 making the number of carbon atoms equal to or more than the lower limit, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and by making the number of carbon atoms equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

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

Examples of the substituent that the alkoxy 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 carboxy group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkyl sulfide group in R ⁶ 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 more than the lower limit, lipophilicity tends to be improved and solubility in solvents tends to be improved, and by making the number of carbon atoms equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

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

Examples of the substituent that the alkyl group in the alkyl sulfide 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 carboxy group, an acryloyl group, and a methacryloyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

^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 hydroxy group, a carboxy group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkylsulfide group which may have a substituent. Among these, from the viewpoint of developability, a hydroxy group or a carboxy group is preferred, and a carboxy group is more preferred.

In formula (III), t represents an integer from 0 to 5, and from the viewpoint of ease of manufacture, it is preferable that t is 0.

When the (c1) acrylic copolymer resin has a partial structure represented by formula (III), the content ratio of the partial structure represented by formula (III) in the (c1) acrylic copolymer resin 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 also 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, there is a tendency that the heat resistance is improved and the decrease in brightness is suppressed, and by setting it to the upper limit or less, there is a tendency that the content ratio of other partial structures increases and the alkali solubility is improved. The above upper and lower limits can be combined arbitrarily. For example, the content ratio of the partial structure represented by formula (III) in the (c1) acrylic copolymer resin is preferably 1 to 50 mol%, more preferably 2 to 40 mol%, even more preferably 5 to 30 mol%, and particularly preferably 8 to 20 mol%.

　(c1) When the acrylic copolymer resin has a partial structure represented by formula (I), it is also preferable that the acrylic copolymer resin has a partial structure represented by the following general formula (IV) as another partial structure contained therein, from the viewpoint of developability.

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

When the (c1) acrylic copolymer resin has a partial structure represented by formula (IV), the content ratio of the partial structure represented by formula (IV) in the (c1) acrylic copolymer resin 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 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 more than the lower limit, there is a tendency for the alkali solubility to be improved, and by making it equal to or less than the upper limit, there is a tendency for the storage stability of the colored resin composition to be improved. The above upper and lower limits can be arbitrarily combined. For example, the content ratio of the partial structure represented by formula (IV) in the (c1) acrylic copolymer resin is preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

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 making it equal to or more than the lower limit, the alkali solubility tends to be improved, and by making it equal to or less than the upper limit, the storage stability of the colored resin composition tends to be improved.
The above upper and lower limits can be combined in any combination. 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.

(C) The weight average molecular weight (Mw) of the alkali-soluble resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, even more preferably 6000 or more, still more preferably 7000 or more, and particularly preferably 8000 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 above the lower limit value, there is a tendency for heat resistance and coating film curing properties to be improved, and by making it below the upper limit value, there is a tendency for alkali solubility to be improved. The above upper and lower limits can be combined in any manner. For example, the weight average molecular weight 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 especially 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 preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less, based on the total solid content of the colored resin composition. By setting the content to be equal to or greater than the lower limit, the coating film curing property upon exposure to ultraviolet light tends to be improved, and by setting the content to be equal to or less than the upper limit, the developer solubility tends to be improved and residues tend to be suppressed. The upper and lower limits can be arbitrarily combined. For example, the content of the alkali-soluble resin (C) in the colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and even more preferably 30 to 50% by mass, based on the total solid content of the colored resin composition.

[2-2] (D) Photopolymerization Initiator The colored resin composition of the present invention contains (D) a photopolymerization initiator. By containing (D) a photopolymerization initiator, film curing properties 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 an additive such as a sensitizing dye, which is added as necessary. 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.

(D) Examples of photopolymerization initiators include metallocene compounds including titanocene compounds described in Japanese Patent Application Publication Nos. 59-152396 and 61-151197, hexaarylbiimidazole derivatives described in Japanese Patent Application Publication No. 10-39503, 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, α-aminoalkylphenone compounds, and oxime ester initiators described in Japanese Patent Application Publication No. 2000-80068.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
Halomethylated triazine derivatives such as 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;

halomethylated oxadiazole derivatives such as 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;
Imidazole derivatives such as 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;
benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone;

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

Benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9-(p-methoxyphenyl)acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Titanocene derivatives such as dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl, dicyclopentadienyl-Ti-2,6-difluorophenyl, dicyclopentadienyl-Ti-2,4-difluorophenyl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl, and dicyclopentadienyl-Ti-2,6-difluoro-3-(pyrrol-1-yl)-phenyl;

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, 4-(diethylamino)chalcone and other α-aminoalkylphenone compounds;
Oxime ester compounds such as 1,2-octanedione-1-[4-(phenylthio)phenyl]-2-(O-benzoyloxime)ethanone and 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime).

From the viewpoints of sensitivity and surface properties, oxime ester compounds (oxime ester photopolymerization initiators) are preferred.
Since the oxime ester compound has a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals, it has high sensitivity even in a small amount and is stable against thermal reactions, and it is possible to design a colored resin composition that has high sensitivity even in a small amount. In particular, from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, an oxime ester compound having a carbazole ring that may have a substituent is preferred.

An example of an oxime ester compound is a compound represented by the following general formula (I-1):

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

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

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

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

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

Examples of the substituents that the carbazolyl group may have include alkyl groups having 1 to 10 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 10 carbon atoms, such as methoxy and ethoxy groups; 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; CN groups; aryloyl groups which may have a substituent; heteroaryloyl groups which may have a substituent; and thenoyl groups which may have a substituent.

The number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the alkanoyl group is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, even more preferably 2 to 5, and particularly preferably 3 to 5.
Examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, and a butanoyl group.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group, and from the viewpoint of ease of synthesis, it is preferable that the alkanoyl group is unsubstituted.

The number of carbon atoms in the aryloyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the aryloyl group is preferably 7 to 20, more preferably 7 to 15, even more preferably 7 to 10, and particularly preferably 8 to 10.
Examples of the aryloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the aryloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amido group, and an alkyl group, and from the viewpoint of ease of synthesis, it is preferable that the aryloyl group is unsubstituted.

As a compound represented by formula (I-1), from the viewpoint of light absorption for the i-line (365 nm) of the exposure light source, compounds represented by the following general formula (I-2) or (I-3) can be mentioned.

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

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

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

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

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

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

Commercially available oxime ester compounds include, for example, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Changzhou New Power Electronic Materials Co., Ltd., and N-1919, NCI-930, and NCI-831 manufactured by ADEKA.

Specific examples of oxime ester compounds include the following:

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

In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (D) is not particularly limited, but is preferably 0.5% by mass or more, 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 also preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably 8% by mass or less, and particularly preferably 7% by mass or less. By making it equal to or more than the lower limit, the curing property of the coating film tends to be improved, and by making it equal to or less than the upper limit, the visible light absorption is reduced, and the brightness tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, in the colored resin composition, the content ratio of the photopolymerization initiator (D) is preferably 0.5 to 10% by mass, more preferably 0.8 to 9% by mass, even more preferably 1.0 to 8% by mass, and particularly preferably 1.2 to 7% by mass, based on the total solid content of the colored resin composition.
In the colored resin composition of the present invention, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of the (D) photopolymerization initiator. Also, 0.05 parts by mass or more is preferable, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, and particularly preferably 0.2 parts by mass or more. By setting it to the upper limit or less, the coating film curability tends to be increased and patterning tends to be improved, and by setting it to the lower limit or more, the change in sensitivity over time tends to be suppressed. The above upper and lower limits can be arbitrarily combined, and for example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.2 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the (D) photopolymerization initiator.

When the colored resin composition of the present invention contains a chain transfer agent, its content is not particularly limited, but is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, particularly preferably 0.4 mass% or more, and is preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and particularly preferably 1 mass% or less, based on the total solid content of the colored resin composition. By making it equal to or more than the lower limit, the solvent resistance tends to be improved, and by making it equal to or less than the upper limit, the storage stability tends to be improved.
The above upper and lower limits can be combined in any combination. For example, when the colored resin composition contains a chain transfer agent, the content ratio is preferably 0.1 to 5 mass%, more preferably 0.2 to 3 mass%, further preferably 0.3 to 2 mass%, and particularly preferably 0.4 to 1 mass%, based on the total solid content of the colored resin composition.

[2-3] Other Solid Contents The colored resin composition of the present invention may further contain solid contents other than the above components, if necessary.
Such components include photopolymerizable monomers, surfactants, and the like.

[2-3-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound"). 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. The monomer in the present invention means a concept opposite to the so-called polymeric substance, and means a concept including dimers, trimers, and oligomers in addition to monomers in the narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds 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. The upper and lower limits can be arbitrarily combined. For example, it may be 2 to 8, 4 to 8, or 5 to 7. By setting it to the lower limit or more, there is a tendency for high sensitivity, and by setting it to the upper limit or less, there is a tendency for solubility in a solvent to be improved.

Examples of ethylenic compounds include unsaturated carboxylic acids and their esters with 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 with polyvalent 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.

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, 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. In addition, examples of the acrylic acid portion of these acrylates include methacrylic acid esters in which the acrylic acid portion 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, such as 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, or 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; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, etc., with (meth)acryloyl group-containing hydroxy compounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, 3-hydroxy(1,1,1-trimethacryloyloxymethyl)propane, etc.

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

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. Furthermore, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as a monomer, if necessary.
The preferred acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. By setting it to the lower limit or more, there is a tendency that the development solubility characteristics can be improved, and by setting it to the upper limit or less, there is a tendency that the production and handling are improved and the curing properties such as photopolymerization performance and pixel surface smoothness are easily improved. 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 of the entire polyfunctional monomer to be within the above range.

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

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 the 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 preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% 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 to be equal to or greater than the lower limit, the curing property of the coating film tends to be improved, and by setting the content to be equal to or less than the upper limit, the flatness of the coating film surface tends to be ensured. The upper and lower limits can be arbitrarily combined. For example, it may be 5 to 60% by mass, 8 to 50% by mass, 10 to 45% by mass, or 12 to 40% by mass.

[2-3-2] Surfactant Various types of surfactants can be used, such as anionic, cationic, nonionic, and amphoteric surfactants. However, it is preferable to use a nonionic surfactant, since it is less likely to adversely affect various properties.

When the colored resin composition of the present invention contains a surfactant, the content of the surfactant is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and is usually 10% by mass or less, preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by 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, it may be 0.001 to 10% by mass, 0.01 to 1% by mass, 0.05 to 0.5% by mass, or 0.1 to 0.3% by mass.

[2-4] Preparation of Colored Resin Composition A method for preparing a colored resin composition (hereinafter, sometimes referred to as a resist) according to the present invention will be described.

The prepared colorant-containing liquid can be further mixed with (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and other components as necessary, to obtain a colored resin composition as a homogeneous solution.

It is preferable that the compound represented by formula (3) and the benzoquinone-based compound in the present invention are already mixed at the time of preparing the colorant-containing liquid.
Specifically, it is preferable to add the compound represented by formula (3) and/or a benzoquinone-based compound in the step of preparing the colorant-containing liquid.

[3] Colored resin composition (second embodiment)
Another embodiment of the colored resin composition of the present invention comprises, as essential components, (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound represented by formula (3) and/or a benzoquinone-based compound, and may further contain, if necessary, other additives other than the above components.

[3-1] (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 absorbency.

The colorant (A) in the colored resin composition of the present invention contains a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter, may be referred to as "phthalocyanine compound (1)"). By containing phthalocyanine compound (1), the transmittance is improved, resulting in a colored resin composition with high brightness.

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

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

Of A ¹ to A ¹⁶ , 6 or more are preferably fluorine atoms, more preferably 7 or more, and even more preferably 8 or more. Also, it is preferably 15 or less, more preferably 12 or less, and even more preferably 10 or less. By making it equal to or more than the lower limit, the stability of the phthalocyanine compound (1) tends to be improved, and by making it equal to or less than the upper limit, the affinity with the dispersant and the 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, the number of substituents representing fluorine atoms among A ¹ to A ¹⁶ is 1 to 15, preferably 6 to 12, and more preferably 7 to 10.

The alkyl groups contained in these groups may be linear, branched, or cyclic, and are 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 it equal to or more than the lower limit, aggregation tends to be suppressed, and foreign matter tends to be suppressed. In addition, by making it 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, 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, and a hexyl group. From the viewpoint of suppressing aggregation, the methyl group and the ethyl group are preferred, and the ethyl group is more preferred.

In formula (1), one or more of A ¹ to A ¹⁶ represent a group represented by formula (2). From the viewpoint of solubility in an organic solvent and brightness, it is preferable that one or more of A ¹ to A ⁴ are groups represented by formula (2), one or more of A ⁵ to A ⁸ are groups represented by formula (2), one or more of A ⁹ to A ¹² are groups represented by formula (2), and one or more of A ¹³ to A ¹⁶ are groups represented by formula (2); it is more preferable that two or more of A ¹ to A ⁴ are groups represented by formula (2), two or more of A ⁵ to A ⁸ are groups represented by formula (2), two or more of A ⁹ to A ¹² are groups represented by formula (2), and two or more of A ¹³ to A ¹⁶ are groups represented by formula (2).

In the above formula (1), one or more of A ¹ to A ¹⁶ represent a fluorine atom. From the viewpoint of stability of the phthalocyanine compound, it is preferable that one or more of A ¹ to A ⁴ are fluorine atoms, one or more of A ⁵ to A ⁸ are fluorine atoms, one or more of A ⁹ to A ¹² are fluorine atoms, and one or more of A ¹³ to A ¹⁶ are fluorine atoms; it is more preferable that two or more of A ¹ to A ⁴ are fluorine atoms, two or more of A ⁵ to A ⁸ are fluorine atoms, two or more of A ⁹ to A ¹² are fluorine atoms, and two or more of A ¹³ to A ¹⁶ are fluorine atoms.

From the viewpoints of the maximum transmission wavelength and transmittance of the phthalocyanine compound (1), the affinity with the dispersant and solvent in the colored resin composition, the uniformity of crystallization of the phthalocyanine compound during baking of the color filter, and the color tone required for the color filter, it is particularly preferable that A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ , and A ¹⁵ are groups represented by formula (2) and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ , and A ¹⁶ are fluorine atoms.

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

In the above formula, Et stands for ethyl.

The (A) colorant may contain other colorants in addition to the phthalocyanine compound (1). Examples of other colorants include dyes and pigments other than the phthalocyanine compound (1). 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.

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, particularly preferably 15% 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, and particularly preferably 50% 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, and by setting the content at or below the upper limit, patterning characteristics and stability over time tend to be ensured. The upper and lower limits can be arbitrarily combined. For example, the content of the colorant (A) in the colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, even more preferably 10 to 60% by mass, and even more preferably 15 to 50% by mass, based on the total solid content of the colored resin composition.

The content of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, 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 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less. By setting it to the lower limit or more, there is a tendency to improve the brightness, and by setting it to the upper limit or less, there is a tendency to ensure the patterning characteristics and stability over time. The above upper and lower limits can be arbitrarily combined. For example, the content of the phthalocyanine compound (1) in the colored resin composition is preferably 1 to 90% by mass, more preferably 3 to 80% by mass, more preferably 5 to 80% by mass, even more preferably 10 to 70% by mass, and even more preferably 15 to 60% by mass.

When the colored resin composition of the present invention contains other colorants, the content ratio 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 also 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 making it equal to or more than the lower limit, a wide range of hues tends to be reproduced, and 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 combination. For example, the content of the other colorant in the colored resin composition is preferably 1 to 30 mass% of the total solid content of the colored resin composition, 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%.

[3-2] (B) Solvent The (B) solvent has a function of dissolving or dispersing the (A) colorant, the (C) alkali-soluble resin, the (D) photopolymerization initiator, the (E) polymerization inhibitor, and other components in the colored resin composition of the present invention, and of adjusting the viscosity.
The solvent (B) may be any solvent capable of dissolving or dispersing each of the components.

When forming pixels of a color filter by photolithography, it is preferable to select a solvent having a boiling point in the range of 100 to 200°C (under a pressure condition of 1013.25 [hPa]. The same applies to all boiling points below.) More preferably, the solvent has a boiling point of 120 to 170°C.
Glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, etc. in the above-mentioned solvents and because 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. Among them, propylene glycol monomethyl ether is particularly preferred from the viewpoint of the solubility of the components in the composition. Glycol monoalkyl ethers have high polarity, and if too much is added, the pigments tend to aggregate, and the viscosity of the colored resin composition obtained later tends to increase, decreasing the storage stability. Therefore, the proportion of glycol monoalkyl ethers in the (B) solvent is preferably 5% to 30% by mass, more preferably 5% to 20% by mass.

In another embodiment, a solvent having a boiling point of 150° C. or higher can be used in combination.
By using a solvent having a boiling point of 150 ° C. or more in combination, the colored resin composition is less likely to dry, but there is an effect of making it difficult for the mutual relationship of the components in the colorant-containing liquid to be destroyed due to rapid drying. When using a solvent having a boiling point of 150 ° C. or more in combination, the content ratio of the solvent having a boiling point of 150 ° C. or more in the (B) solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it to the lower limit or more, for example, there is a tendency to easily avoid the color material components and the like precipitating and solidifying at the tip of the slit nozzle, causing foreign matter defects, and by setting it to the upper limit or less, there is a tendency to easily avoid the drying speed of the composition being slowed down, causing problems such as poor tact in the reduced pressure drying process and pin marks in the pre-bake.
The solvent having a boiling point of 150° C. or higher may be either a glycol alkyl ether acetate or a glycol alkyl ether. In this case, it is not necessary to separately contain a solvent having a boiling point of 150° C. or higher.
Preferred examples of the solvent 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.

In color filter manufacturing using the inkjet method, the ink discharged from the nozzle is very fine, at several to several tens of pL, so the solvent tends to evaporate and the ink tends to concentrate and dry up before landing around the nozzle opening or inside the pixel bank. In order to avoid this, it is preferable that the (B) solvent contains a solvent with a high boiling point, specifically, a solvent with a boiling point of 180°C or higher. It is more preferable that the (B) solvent contains a solvent with a boiling point of 200°C or higher, and it is particularly preferable that the (B) solvent contains a solvent with a boiling point of 220°C or higher. When a solvent with a boiling point of 180°C or higher is used in combination, the content of the solvent with a boiling point of 180°C or higher in the (B) solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more. By setting the content at or above the lower limit, the effect of preventing the evaporation of the solvent from the droplets tends to be fully exerted.

Examples of solvents having a boiling point of 180° C. or higher include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and triacetin, among the various solvents mentioned above.
In order to adjust the viscosity of the colored resin composition and the solubility of the solid content, it is effective to partially contain a solvent having a boiling point lower than 180° C. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, for example, ethers, esters, and ketones are preferable. Among them, for example, cyclohexanone, dipropylene glycol dimethyl ether, and cyclohexanol acetate are preferable.

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

[3-3] (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.

By adding an unsaturated monobasic acid to the epoxy group, it is possible to impart polymerizability to the resin (C-1).
The unsaturated monobasic acid is added to the copolymer of the epoxy resin-containing (meth)acrylate and other radically polymerizable monomer in an amount of usually 10 to 100 mol %, preferably 30 to 100 mol %, more preferably 50 to 100 mol %, assuming that the total epoxy groups of the copolymer of the epoxy resin-containing (meth)acrylate and other radically polymerizable monomer are 100 mol %. By making the amount equal to or more than the lower limit, the colored resin composition tends to have good stability over time.
As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

The aromatic ring group in R ⁴ includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, and is preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. By making the number of carbon atoms equal to or more than the lower limit, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and by making the number of carbon atoms equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The above upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms in the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, even more preferably 6 to 20, and particularly preferably 6 to 18.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, 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.
In addition, the aromatic heterocycle in the aromatic heterocycle group may be a single ring or a condensed ring, and examples thereof include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.From the viewpoint of development property, benzene ring group and naphthalene ring group are preferred, and benzene ring group 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 carboxy group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkynyl group in R ⁶ 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 to be equal to or more than the lower limit, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and by setting the number of carbon atoms to be equal to or less than the upper limit, hydrophilicity tends to be improved and alkali solubility tends to be improved. The upper and lower limits can be arbitrarily combined. For example, the number of carbon atoms of the alkynyl group is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.

In formula (III), t represents an integer from 0 to 5, but from the viewpoint of ease of manufacture, it is preferable that t is 0.

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

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

[3-4] (D) Photopolymerization Initiator The colored resin composition of the present invention contains (D) a photopolymerization initiator. By containing (D) a photopolymerization initiator, film curing properties 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 an additive such as a sensitizing dye, which is added as necessary. 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 preferably contains a photopolymerization initiator (d1) represented by the following general formula (DI) (hereinafter, sometimes referred to as "photopolymerization initiator (d1)"). The photopolymerization initiator (d1) has a low-reactivity indole ring bonded to the (keto)oxime ester group, and therefore the decomposition and reaction speed is slow, allowing radicals to be generated intermittently, and radical deactivation by the dye is suppressed, allowing high curability to be maintained. Therefore, even in a situation where the prebake temperature is in the low temperature range, there is a large amount of residual solvent and the sensitivity is low, it is possible to suppress the penetration of the developer into the coating film, and it is believed that the effect of temperature changes in the prebake on sensitivity can be reduced.

In formula (DI), 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 formula (DI), R ^d1 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group in R ^d1 may be linear, branched, cyclic, or a combination 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 making the number of carbon atoms in the alkyl group equal to or less than the upper limit, solubility in a solvent 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, the alkyl group is preferably unsubstituted.

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 in the aromatic ring group 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 more than the lower limit, the molecule tends to be stable, and by making the number of carbon atoms equal to or less than the upper limit, the solvent solubility tends to be good.

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 of which has one free valence.
The aromatic heterocycle in the aromatic heterocycle group may be a single ring or a condensed ring.The aromatic heterocycle group may be, for example, 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, or an azulene ring, each of which has one free valence.
From the viewpoint of solvent solubility, the aromatic heterocyclic group is preferably a benzene ring or a naphthalene ring having one free valence, and more preferably a benzene ring having one free valence.

Examples of the substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, a hydroxyl group, and a nitro group. From the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms and a hydroxyl group are preferred.

From the viewpoints of solubility in a solvent and ease of synthesis, R 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 formula (DI), R ^d2 represents an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.
The alkyl group in R ^d2 may be linear, branched, cyclic, or a combination thereof, but is preferably linear or branched from the viewpoint of solvent solubility, more preferably linear, while an unsubstituted linear alkyl group is preferred from the viewpoint of sensitivity.

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, even 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 making the number of carbon atoms in the alkyl group equal to or more than the lower limit, sensitivity tends to improve, and by making the number of carbon atoms equal to or less than the upper limit, solvent affinity tends to improve. The upper and lower limits above can be combined in any combination. For example, it may be 1 to 12, 2 to 12, 3 to 10, 4 to 10, 5 to 9, or 6 to 8.

Examples of the 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 viewpoint of solvent solubility, alkoxy groups having 1 to 3 carbon atoms are preferred. Also, from the viewpoint of ease of synthesis, unsubstituted groups are preferred.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl. Among these, from the viewpoints 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 in the aromatic ring group 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 more than the lower limit, the molecule tends to be stable, and by making the number of carbon atoms in the aromatic ring group equal to or less than the upper limit, the solvent solubility tends to be good. The above upper and lower limits can be combined arbitrarily. For example, it may be 4 to 12, 4 to 10, or 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 of which has one free valence.
The aromatic heterocycle in the aromatic heterocycle group may be a single ring or a condensed ring. Examples of the aromatic heterocycle 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 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 the 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 viewpoint of solvent solubility, alkoxy groups having 1 to 5 carbon atoms and hydroxyl groups are preferred. 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 viewpoints 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 formula (DI), 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 in the aromatic ring group 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 more than the lower limit, the sensitivity during exposure tends to be improved, and by making the number of carbon atoms equal to or less than the upper limit, the solvent affinity tends to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 4 to 12, 4 to 10, or 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 of which has one free valence.
The aromatic heterocycle in the aromatic heterocycle group may be a single ring or a condensed ring. Examples of the aromatic heterocycle 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 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 the substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aryloyl group having 6 to 10 carbon atoms, halogen atoms such as F, Cl, Br, and I, a hydroxyl group, and a nitro group. From the viewpoint of sensitivity during exposure, an aryl group having 6 to 10 carbon atoms and an aryloyl group 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 a benzene ring group having one free valence and which may have a substituent.

(p)
In formula (DI), p represents 0 or 1. From the viewpoint of sensitivity, p is preferably 0, while p is preferably 1 from the viewpoint of suppressing residues by improving solvent affinity.

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

In formula (DII), R ^d1 , R ^d2 and p are the same as defined in formula (DI).
R ^d4 represents any monovalent substituent. q represents an integer of 0 to 3.

(R ^d4 )
In formula (DII), R ^d4 represents any monovalent substituent.
Examples of the arbitrary 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; CN groups; benzoyl groups which may have a substituent; and thenoyl groups which may have a substituent. 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 may have 0 to 3 of them. From the viewpoint of sensitivity, nitro groups, CN groups, benzoyl groups which may have a substituent, and thenoyl groups which may have a substituent are preferred, and the benzoyl group is more preferred.
In R ^d4 , when q is 2 or more, a plurality of R ^d4 may be bonded together to form a ring. The ring 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 formula (DII), q represents an integer of 0 to 3. From the viewpoints of suppressing residues due to improved solubility in a solvent and improving sensitivity during exposure, q is preferably 0 or 1, and more preferably 1.

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 described in JP-A-2000-80068 and JP-A-2006-36750.

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

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 the oxime ester derivatives include the oxime ester compounds described in JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, and JP-A-2012-519191. From the viewpoint of sensitivity, methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate is preferred, and product names such as 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) are preferred.
The other photopolymerization initiators (d2) may be used alone or in combination of two or more.

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

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 them to another compound.
As the chain transfer agent, various compounds having the above-mentioned functions can be used, but examples include mercapto group-containing compounds and carbon tetrachloride, and it is more preferable to use mercapto group-containing compounds because they tend to have a high chain transfer effect. This is thought to be because the S-H bond energy is small, so bond cleavage is likely to occur, and hydrogen abstraction reactions and chain transfer reactions are likely to occur. It is effective in improving sensitivity and surface hardening.

Examples of mercapto group-containing compounds include mercapto group-containing compounds having aromatic rings 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. Examples of the mercapto group-containing aliphatic compounds include lysthioglycolate, 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.

As mercapto group-containing compounds having an aromatic ring, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred, and as 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.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferred, and trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), 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, and pentaerythritol tetrakis(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptobutyrate) are more preferred.
These may be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content of the photopolymerization initiator (D) 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 preferably 10% by mass or less, more preferably 9% by mass or less, even more preferably 8% by mass or less, and particularly preferably 7% 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, the curing property of the coating film tends to be improved, and by setting the content at or below the upper limit, the visible light absorption is reduced, and the brightness tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content of the photopolymerization initiator (D) is preferably 0.5 to 10% by mass, more preferably 0.8 to 9% by mass, even more preferably 1.0 to 8% by mass, and particularly preferably 1.2 to 7% by mass, based on the total solid content of the colored resin composition.

When the colored resin composition of the present invention contains a photopolymerization initiator (d1), the content of the photopolymerization initiator (d1) in the colored resin composition 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 7% by mass or less, more preferably 5% by mass or less, even more preferably 4% by mass or less, and particularly preferably 3% by mass or less, based on the total solid content of the colored resin composition. By setting the content to be equal to or greater than the lower limit, the coating film curing property during low-temperature pre-baking tends to be improved, and by setting the content to be equal to or less than the upper limit, the visible light absorption is reduced, and the brightness tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, in the colored resin composition, the content of the photopolymerization initiator (d1) is preferably 0.5 to 7% by mass, more preferably 0.8 to 5% by mass, even more preferably 1.0 to 4% by mass, and particularly preferably 1.2 to 3% by mass, based on the total solid content of the colored resin composition.

When the colored resin composition of the present invention contains a chain transfer agent, the content is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, particularly preferably 0.4% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less, based on the total solid content of the colored resin composition. By setting the content to be equal to or greater than the lower limit, there is a tendency for the solvent resistance to be improved, and by setting the content to be equal to or less than the upper limit, there is a tendency for the storage stability to be improved. The upper and lower limits can be arbitrarily combined. For example, when the colored resin composition contains a chain transfer agent, the content is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, even more preferably 0.3 to 2% by mass, and particularly preferably 0.4 to 1% by mass, based on the total solid content of the colored resin composition.

[3-5] Compound represented by formula (3) and benzoquinone-based compound The colored resin composition of the present invention contains a compound represented by the following general formula (3) and/or a benzoquinone-based compound.

Phthalocyanine compound (1) has a fluorine atom with a very large electronegativity, so it has a high molecular polarity and is considered to have a high affinity with the compound represented by formula (3) and benzoquinone-based compounds. In addition, phthalocyanine compounds generally have a high molecular planarity, and among them, phthalocyanine compound (1) has a fluorine atom with a very small atomic radius, so it is considered to have a small steric hindrance of the molecule and a high affinity with the compound represented by formula (3) and benzoquinone-based compounds. Therefore, the colored resin composition of the present invention contains a compound represented by formula (3) and/or a benzoquinone-based compound, so that the phthalocyanine compound (1) and the compound represented by formula (3) and the benzoquinone-based compound are present in close proximity to each other in the colored resin composition, and the phthalocyanine compound (1) approaches the photopolymerization initiator (D) and the phthalocyanine compound (1) interacts with the photopolymerization initiator (D), which is considered to suppress the decrease in the polymerization ability and film curing ability of the photopolymerization initiator (D).

Examples of the compound represented by formula (3) include hydroquinones such as methylhydroquinone (MHQ), phenols such as 4-methoxyphenol (MEHQ) and dibutylhydroxytoluene (BHT), and hindered phenols such as pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate].
An example of the benzoquinone compound is 1,4-benzoquinone.
Among the compounds represented by formula (3) and the benzoquinone-based compounds, from the viewpoint of affinity with the phthalocyanine compound (1), specifically, from the viewpoint of molecular polarity and steric hindrance of the molecule, methylhydroquinone (MHQ), 4-methoxyphenol (MEHQ), dibutylhydroxytoluene (BHT), and pentaerythritol tetrakis[3-[3,5-di(tert-butyl)-4-hydroxyphenyl]propionate] are preferred, and methylhydroquinone (MHQ) and 4-methoxyphenol (MEHQ) are particularly preferred.
The compound represented by formula (3) and the benzoquinone-based compound may be used alone or in combination of two or more kinds.

The total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.80 mass% or less, more preferably 0.50 mass% or less, even more preferably 0.30 mass% or less, and particularly preferably 0.10 mass% or less, based on the total solid content of the colored resin composition. Also, it is preferably 0.001 mass% or more, more preferably 0.02 mass% or more, even more preferably 0.03 mass% or more, and particularly preferably 0.05 mass% or more. By making it equal to or greater than the lower limit, there is a tendency for the effect of suppressing the interaction between the phthalocyanine compound (1) and the photopolymerization initiator to be improved. Also, by making it equal to or less than the upper limit, there is a tendency for a pattern with high curability and good linearity to be formed. The upper and lower limits above can be combined in any combination. For example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.001 to 0.80% by mass, more preferably 0.02 to 0.50% by mass, even more preferably 0.03 to 0.10% by mass, and particularly preferably 0.05 to 0.10% by mass, based on the total solid content of the colored resin composition.

In the colored resin composition of the present invention, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 5 parts by mass or less, relative to 100 parts by mass of (D) photopolymerization initiator. Also, 0.05 parts by mass or more is preferable, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, and particularly preferably 0.2 parts by mass or more. By setting it to the upper limit or less, the coating film curability tends to be increased and patterning tends to be improved, and by setting it to the lower limit or more, the change in sensitivity over time tends to be suppressed. The above upper and lower limits can be arbitrarily combined. For example, the total content of the compound represented by formula (3) and the benzoquinone-based compound is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, even more preferably 0.2 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of (D) photopolymerization initiator.

[3-6] Other Solid Contents The colored resin composition of the present invention may further contain solid contents other than the above components, if necessary.
Such components include photopolymerizable monomers, dispersants, dispersion aids, surfactants, and the like.

[3-6-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular compound, but is preferably an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound"). 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. The monomer in the present invention means a concept opposite to the so-called polymeric substance, and means a concept including dimers, trimers, and oligomers in addition to monomers in the narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds 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. The upper and lower limits can be arbitrarily combined. For example, it may be 2 to 8, 4 to 8, or 5 to 7. By setting it to the lower limit or more, there is a tendency for high sensitivity, and by setting it to the upper limit or less, there is a tendency for solubility in a solvent to be improved.

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, 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. In addition, examples of the acrylic acid portion of these acrylates include methacrylic acid esters in which the acrylic acid portion is replaced with a methacrylic acid portion, itaconic acid esters in which the itaconic acid portion is replaced with a crotonic acid ester, and maleic acid esters in which the maleic acid portion is replaced with a maleic acid portion.

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 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 setting the content to be equal to or greater than the lower limit, the curing property of the coating film tends to be improved, and by setting the content to be equal to or less than the upper limit, the flatness of the coating film surface tends to be ensured. The upper and lower limits can be arbitrarily combined. For example, it may be 5 to 60% by mass, 8 to 50% by mass, 10 to 45% by mass, or 12 to 40% by mass.

[3-6-2] Dispersant, Dispersing Aid When the colored resin composition of the present invention contains a pigment as the colorant (A), it is preferable to contain a dispersant for the purpose of stably dispersing the pigment. Among the dispersants, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time.
Examples of the polymer dispersant 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 the polymer dispersant include, by trade name, EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparlon (registered trademark, manufactured by Kusumoto Chemical Industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and polymer dispersants described in JP 2013-119568 A.

The number of carbon atoms in the aralkyl group, which may have a substituent, in formula (11) is not particularly limited, but is usually 7 or more, and preferably 16 or less, more preferably 12 or less, and even more preferably 9 or less. Examples of aralkyl groups include phenylmethylene groups, phenylethylene groups, phenylpropylene groups, phenylbutylene groups, and phenylisopropylene groups, with phenylmethylene groups, phenylethylene groups, phenylpropylene groups, and phenylbutylene groups being preferred, and phenylmethylene groups and phenylethylene groups being more preferred.

These ring structures may further have substituents.

The block copolymer can be produced by known methods, for example, by living polymerization of monomers that introduce the above-mentioned respective repeating units.
Living polymerization methods are described in Japanese Patent Application Laid-Open Nos. 9-62002 and 2002-31713, as well as P. Lutz, P. Masson et al., Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al., Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al., Polym. J. 17, 977 (1985), K. Hatada, K. Ute, et al., Polym. J. 18, 1037 (1986), Koichi Migite, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Research Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthesis Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Hertler et al., Macromolecules, 20, 1473 (1987) 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 preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% 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, there is a tendency for dispersibility and storage stability to be improved, and by setting the content at or below the upper limit, there is a tendency for electrical reliability and developability to be improved. The upper and lower limits can be arbitrarily combined. For example, it may be 0.001 to 25% by mass, 0.01 to 20% by mass, 0.1 to 15% by mass, or 1 to 10% by mass or more.

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, even more preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, relative to 100 parts by mass of the pigment, 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, and particularly preferably 30 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, it may be 0.5 to 70 parts by mass, 5 to 70 parts by mass, 10 to 50 parts by mass, 15 to 40 parts by mass, or 20 to 30 parts by mass. By keeping it within the above range, it tends to be possible to obtain a colored resin composition with excellent dispersion stability and high brightness.

When the colored resin composition of the present invention contains a pigment, it may contain a pigment derivative or the like as a dispersing aid to improve the dispersibility and dispersion stability of the pigment. Examples of pigment derivatives include 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 pigment derivatives. Substituents of the pigment derivative include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxy groups, amide groups, and the like, which are bonded to the pigment skeleton directly or via alkyl groups, aryl groups, heterocyclic groups, and the like, and are preferably sulfonamide groups and quaternary salts thereof, and sulfonic acid groups, and more preferably sulfonic acid groups. These substituents may be substituted in a plurality on one pigment skeleton, or may be a mixture of compounds with different numbers of substitutions. Examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, 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.

[3-6-3] Surfactant Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as the surfactant, but it is preferable to use a nonionic surfactant because it is less likely to adversely affect various properties. The content of the surfactant is not particularly limited, but is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is usually 10% by mass or less, preferably 1% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less in the total solid content of the colored resin composition. The upper and lower limits above can be combined arbitrarily. For example, it may be 0.001 to 10% by mass, 0.01 to 1% by mass, 0.05 to 0.5% by mass, or 0.1 to 0.3% by mass.

[3-7] Preparation of Colored Resin Composition A method for preparing a colored resin composition (hereinafter, sometimes referred to as a resist) according to the present invention will be described.

When dispersing a colorant, the colorant, solvent, and dispersant are weighed out in predetermined amounts, and in the dispersion process, the colorant is dispersed to prepare a colorant-containing liquid. In this dispersion process, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. can also be used. This dispersion process breaks down the colorant into fine particles, improving the application characteristics of the colored resin composition and improving the transmittance of pixels in the finished color filter substrate.

When dispersing the colorant, it is preferable to use a dispersing aid or a dispersing resin in combination as described above.
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 the dispersion treatment is usually set to 0° C. or higher, preferably room temperature or higher, and usually 100° C. or lower, preferably 80° C. or lower. The dispersion time may be adjusted appropriately since the appropriate time varies depending on the composition of the colorant-containing liquid and the size of the sand grinder device.

The colorant-containing liquid obtained by the above dispersion process can be mixed with a solvent, an alkali-soluble resin, a photopolymerization initiator, and other components as necessary to obtain a colored resin composition as a homogeneous solution. Note that since fine dust particles may be mixed in during the dispersion process and each mixing process, it is preferable to filter the obtained composition using a filter or the like.

If the colorant is not dispersed, the colorant, solvent, alkali-soluble resin, photopolymerization initiator, and other components as necessary can be mixed to obtain a colored resin composition as a homogeneous solution. It is preferable to filter the obtained composition using a filter or the like.

It is preferable that the compound represented by the formula (3) and the benzoquinone-based compound in the present invention are already mixed with the phthalocyanine compound (1) when the phthalocyanine compound (1) and the photopolymerization initiator are mixed.
Specifically, it is preferable to add the compound represented by the formula (3) and/or the benzoquinone-based compound in the step of preparing a colorant-containing liquid containing the phthalocyanine compound (1) (i.e., before the (D) photopolymerization initiator is added), or to add the phthalocyanine compound (1) and the compound represented by the formula (3) and/or the benzoquinone-based compound before the phthalocyanine compound (1) and the photopolymerization initiator are mixed in the step of preparing a colored resin composition.

[4] Manufacturing of Color Filter Substrate Next, the color filter according to the present invention will be described.
The color filter according to the present invention has pixels formed using the above-mentioned colored resin composition.

[4-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited in material as long as it is transparent and has a suitable strength. Examples of the material 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 resin, unsaturated polyester resin, and poly(meth)acrylic resin, and various glasses. Among these, glass or heat-resistant resins are preferred from the viewpoint of heat resistance.

The transparent substrate and the black matrix-formed substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment with silane coupling agents or various resins such as urethane resins, as necessary, in order to improve surface properties such as adhesion. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When thin film formation treatment with various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

[4-2] Black matrix The color filter according to the present invention can be manufactured by providing a black matrix on the above-mentioned transparent substrate and then forming pixel images, usually red, green, and blue. The above-mentioned colored resin composition is preferably used as a coating liquid for forming a green or blue pixel (resist pattern) among the red, green, and blue pixels. The coating liquid for forming a resist pattern is used to form a pixel image by carrying out each process of coating, heating and drying, image exposure, development, and heat curing on a resin black matrix formed on a transparent substrate or a metal black matrix formed using a chromium compound or other light-shielding metal material.

The black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, metal chromium, chromium oxide, chromium nitride and other chromium compounds, nickel-tungsten alloys, etc., may be used, and these may be laminated in a multi-layer structure.
These metal light-shielding films are generally formed by a sputtering method. After forming a desired pattern in a film shape using positive photoresist, the film is etched using an etching solution of a mixture of ceric ammonium nitrate and perchloric acid and/or nitric acid for chromium, or an etching solution appropriate for the material for other materials. Finally, the positive photoresist is stripped off with a dedicated stripping agent to form a black matrix.

In this case, a thin film of the metal or metal/metal oxide is first formed on a transparent substrate by vapor deposition or sputtering. Next, a coating film of a colored resin composition is formed on this thin film, and the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, or triangles to form a resist image. The coating film is then etched to form a black matrix.

When using a 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, titanium black, or a mixture of red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes can be used to form a black matrix in the same manner as in the method for forming red, green, and blue pixel images described below.

[4-3] 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 then dried. 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, to form a color filter image.

The colored resin composition for color filters can be applied by a method such as the spinner method, wire bar method, flow coating method, die coating method, roll coating method, or spray coating method. Among these, the die coating method is preferable from an overall standpoint, since it significantly reduces the amount of coating solution used, is completely free of the effects of mist that adheres when using spin coating, and also suppresses the generation of foreign matter.

If the thickness of the coating film is too large, it may be difficult to develop the pattern and adjust the gap during the liquid crystal cell formation process, while if the thickness is too small, it may be difficult to increase the pigment concentration and the desired color may not be expressed. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm or less.

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

The temperature conditions for reheating and drying are preferably higher than the pre-drying temperature, and specifically, are usually 50°C or higher, preferably 70°C or higher, and usually 200°C or lower, preferably 160°C or lower, and particularly preferably 130°C or lower. The drying time depends on the heating temperature, but is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or less, and preferably 5 minutes. The higher the drying temperature, the better the adhesion to the transparent substrate, but if the temperature is too high, the binder resin may decompose, inducing thermal polymerization and resulting in poor development. The drying process for this coating film may also be performed using a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

[4-5] Exposure step Image exposure is performed by superposing a negative matrix pattern on the coating film of the colored resin composition, and irradiating a light source of ultraviolet or visible light through this mask pattern. At this time, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, an oxygen barrier layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer before exposure. The light source used for the image exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, and 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.

[4-6] Development process The color filter according to the present invention can be produced by forming an image on a substrate by performing image exposure on a coating film using the colored resin composition according to the present invention using the above-mentioned light source, and then performing development using an aqueous solution containing a surfactant and an alkaline compound. This aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Alkaline compounds include inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, 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, as well as 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 a mixture of two or more kinds.

Surfactants include, for example, 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 alkylbenzene sulfonates, alkylnaphthalene 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, diacetone alcohol, etc. The organic solvent can be used in combination with the 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, and more preferably 20° C. or higher, and usually 50° C. or lower, preferably 45° C. or lower, and more preferably 40° C. or lower. The development method may be any method such as immersion development, spray development, brush development, or ultrasonic development.

[4-7] Heat curing treatment The color filter after development is subjected to heat curing treatment. The heat curing treatment conditions are selected such that the temperature is usually 100°C or higher, preferably 150°C or higher, and usually 280°C or lower, preferably 250°C or lower, and the time is selected in the range of 5 minutes or more and 60 minutes or less. Through this series of steps, the formation of a patterned image of one color is completed. This process is repeated in sequence to pattern black, red, green, and blue, forming a color filter. The order of patterning the four colors is not limited to the order described above.

[4-8] Formation of Transparent Electrode The color filter according to the present invention is used as a part of a color display, liquid crystal display device, etc. by forming a transparent electrode such as ITO on the image as it is, but in order to improve the surface smoothness and durability, a top coat layer such as polyamide, polyimide, etc. can be provided on the image as necessary. In some applications such as a planar alignment type driving method (IPS mode), a transparent electrode may not be formed.

[5] Image display device (panel)
Next, the image display device of the present invention will be described. The image display device of the present invention has the above-mentioned color filter. Hereinafter, as the image display device, a liquid crystal display device and an organic EL display device will be described in detail.

[5-1] Liquid crystal display device A method for manufacturing a liquid crystal display device according to the present invention will be described. A liquid crystal display device according to the present invention is usually manufactured by forming an alignment film on the color filter according to 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 injected into the formed liquid crystal cell, and the liquid crystal is connected to the opposing electrode to complete the device. A resin film such as polyimide is suitable for the alignment film. A gravure printing method and/or a flexographic printing method is usually used to form the alignment film, and the thickness of the alignment film is set to several tens of nm. After hardening the alignment film by thermal baking, the surface is treated by irradiation with ultraviolet light or treatment with a rubbing cloth to process the surface into a state in which the tilt of the liquid crystal can be adjusted.

The size of the spacer used depends on the gap (gap) with the opposing substrate, and typically 2 to 8 μm is suitable. A photospacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography, and this can also be used in place of the spacer. An array substrate is usually used as the opposing substrate, and a TFT (thin film transistor) substrate is 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 portions other than the liquid crystal injection port are sealed with a sealant such as epoxy resin. The sealant is hardened by UV irradiation and/or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell with the sealed periphery 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 chamber is leaked to inject the liquid crystal into the liquid crystal cell. The degree of reduced pressure in 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. It is also preferable to heat the liquid crystal cell during the reduction in pressure, and the heating temperature is usually 30° C. or more, preferably 50° C. or more, and usually 100° C. or less, preferably 90° C. or less.

The heating and holding time during reduced pressure is usually within a range of 10 minutes to 60 minutes, after which the cell is immersed in liquid crystal. The liquid crystal cell into which the liquid crystal has been injected is sealed at the liquid crystal injection port by curing a UV curable resin, completing the liquid crystal display device (panel).
There is no particular restriction on the type of liquid crystal, and any of the conventionally known liquid crystals such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystals, thermotropic liquid crystals, etc. may be used.
Known thermotropic liquid crystals include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals, and any of these may be used.

[5-2] Organic EL Display Device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, a multi-color organic EL element is produced by laminating an organic light-emitting body 500 on a blue color filter having pixels 20 formed thereon using 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.

The organic light-emitting body 500 can be laminated by sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of a color filter, or by bonding an organic light-emitting body 500 formed on a separate substrate onto an inorganic oxide film 40. The organic EL element 100 thus fabricated can be applied to both passively driven organic EL display devices and actively driven organic EL display devices.

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

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

<Compound A>
Methylhydroquinone (2,5-dihydroxytoluene) was used, which has the following chemical structure: This is a compound represented by formula (3).

<Compound B>
The compound used was 4-methoxyphenol, which has the following chemical structure:

<Compound C>
Dibutylhydroxytoluene (2,6-di-tert-butyl-p-cresol) having the following chemical structure was used: This is a compound represented by formula (3).

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

The content of the repeating units represented by the following formulae (1a) and (2a) in the total repeating units is 33.3 mol % and 6.7 mol %, respectively.

<Alkali-soluble resin A>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen and heated to 120 ° C. 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate, and 10 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were dropped therein, and further stirring was continued for 2 hours at 120 ° C. Next, the inside of the reaction vessel was changed to air replacement, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 50 parts by mass of acrylic acid, and the reaction was continued for 6 hours at 120 ° C. Then, 13 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 in terms of polystyrene measured by GPC of the alkali-soluble resin A thus obtained was 9000, and the acid value was 25 mg KOH / g.

<Alkali-soluble resin B>
A separable flask equipped with a cooling tube 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 temperature of the reaction vessel was raised to 90° C. by heating in an oil bath with stirring.

Meanwhile, 30 parts by mass of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, 5.2 parts by mass of t-butylperoxy-2-ethylhexanoate, and 40 parts by mass of propylene glycol monomethyl ether acetate were charged into the monomer tank, and 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged into the chain transfer agent tank. After the temperature of the reaction tank stabilized at 90°C, dropping was started from the monomer tank and the chain transfer agent tank to start polymerization. Dropping was carried out over 135 minutes while maintaining the temperature at 90°C, and 60 minutes after the end of dropping, 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 mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel, and the mixture was reacted at 110°C for 9 hours.
After cooling to room temperature, an alkali-soluble resin B was obtained, which had a polystyrene-equivalent weight average molecular weight Mw of 9,000, an acid value of 101 mgKOH/g, and a double bond equivalent of 550 g/mol as measured by GPC.

<Alkali-soluble resin C>
A separable flask equipped with a cooling tube 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 temperature of the reaction vessel was raised to 90° C. by heating in an oil bath with stirring.

After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (v/v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged into the reaction vessel, and the mixture was reacted at 110°C for 9 hours.
The mixture was cooled to room temperature, and an alkali-soluble resin C having a weight average molecular weight Mw of 9,000 in terms of polystyrene measured by GPC and an acid value of 101 mgKOH/g was obtained.

<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

<Preparation of Colorant-Containing Liquid 1>
As shown in Table 1, 9.9 parts by mass of phthalocyanine compound A, 0.1 part by mass of dispersant A in terms of solid content, 0.005 part by mass of compound 1, 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 filled into a stainless steel container, and a dispersion treatment was carried out for 6 hours using a paint shaker.
After the dispersion was completed, the beads and the dispersion were separated using a filter to prepare colorant-containing liquid 1.

<Preparation of Colorant-Containing Liquids 2 to 4>
As shown in Table 1, colorant-containing liquids 2 to 4 were prepared in the same manner as colorant-containing liquid 1, except that the amount of compound 1 added was changed to 0.01 parts by mass, 0.099 parts by mass, and 0.495 parts by mass, respectively.

<Preparation of Colorant-Containing Liquids 5 to 8 and Colorant-Containing Liquid 17>
As shown in Table 1, colorant-containing liquids 5 to 8 and colorant-containing liquid 17 were prepared in the same manner as colorant-containing liquid 1, except that compound 2 was used instead of compound 1 and the amounts added were changed to 0.005 parts by mass, 0.01 parts by mass, 0.099 parts by mass, 0.495 parts by mass, and 0.002 parts by mass, respectively.

<Preparation of Colorant-Containing Liquids 9 to 12 and Colorant-Containing Liquid 18>
As shown in Table 1, colorant-containing liquids 9 to 12 and colorant-containing liquid 18 were prepared in the same manner as colorant-containing liquid 1, except that compound 3 was used instead of compound 1 and the amounts added were changed to 0.005 parts by mass, 0.01 parts by mass, 0.099 parts by mass, 0.495 parts by mass, and 0.002 parts by mass, respectively.

<Preparation of Colorant-Containing Liquids 13 and 14>
As shown in Table 1, colorant-containing liquids 13 and 14 were prepared in the same manner as colorant-containing liquid 1, except that the amount of compound 1 added was changed to 0 parts by mass and 0.99 parts by mass, respectively.

<Preparation of Colorant-Containing Liquid 15>
As shown in Table 1, 12.86 parts by mass of C.I. Pigment Green 58, 2.86 parts by mass of dispersant A in terms of solid content, 4.29 parts by mass of alkali-soluble resin A in terms of solid content, 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 alkali-soluble 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 dispersed for 6 hours using a paint shaker. After dispersion was completed, the beads and the dispersion were separated using a filter to prepare colorant-containing liquid 15.

<Preparation of Colorant-Containing Liquid 16>
As shown in Table 1, 12.86 parts by mass of C.I. Pigment Green 59, 2.86 parts by mass of dispersant A in terms of solid content, 4.26 parts by mass of alkali-soluble resin C in terms of solid content, 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 alkali-soluble resin C), and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and dispersed for 6 hours using a paint shaker. After dispersion was completed, the beads and the dispersion were separated using a filter to prepare colorant-containing liquid 16.

<Preparation of green dye-containing solution A>
As shown in Table 2, 9.9 parts by mass of phthalocyanine compound A, 0.1 parts by mass of dispersant A in terms of solid content, 72.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent (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 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 colorant-containing liquid were separated using a filter to prepare green dye-containing liquid A.

<Preparation of Green Pigment-Containing Liquid A>
As shown in Table 2, 12.9 parts by mass of C.I. Pigment Green 58, 2.9 parts by mass of dispersant A in terms of solid content, 4.3 parts by mass of resin A in terms of solid content, 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 alkali-soluble resin C), and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and dispersed for 6 hours using a paint shaker. After dispersion, the beads and the colorant-containing liquid were separated using a filter to prepare green pigment-containing liquid A.

<Preparation of Green Pigment-Containing Liquid B>
As shown in Table 2, 12.9 parts by mass of C.I. Pigment Green 59, 2.9 parts by mass of dispersant A in terms of solid content, 4.3 parts by mass of alkali-soluble resin C in terms of solid content, 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 alkali-soluble resin C), and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and dispersed for 6 hours using a paint shaker. After dispersion, the beads and the colorant-containing liquid were separated using a filter to prepare green pigment-containing liquid B.

<Preparation of Yellow Pigment-Containing Liquid A>
As shown in Table 2, 12.6 parts by mass of C.I. Pigment Yellow 138, 3.2 parts by mass of dispersant A in terms of solid content, 4.2 parts by mass of alkali-soluble resin C in terms of solid content, 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 alkali-soluble resin C), and 225 parts by mass of zirconia beads having a diameter of 0.5 mm were filled into a stainless steel container and dispersed for 6 hours using a paint shaker. After dispersion, the beads and the colorant-containing liquid were separated using a filter to prepare a yellow pigment-containing liquid A.

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

<Photopolymerization initiator A>
An oxime ester compound having the following chemical structure was used.

<Photopolymerization initiator B>
An oxime ester compound having the following chemical structure was used.

<Photopolymerization initiator C>
An oxime ester compound having the following chemical structure was used.

<Photopolymerization initiator D>
An oxime ester compound having the following chemical structure was used.

<Photopolymerization initiator E>
An oxime ester compound having the following chemical structure was used.

<Photopolymerization initiator F>
An oxime ester compound having the following chemical structure was used.

<Surfactant A>
Megafac F-554 (DIC)

<Preparation of Colored Resin Composition>
The components shown in Tables 3 to 5 were mixed in the solid content ratios shown to prepare colored resin compositions. Propylene glycol monomethyl ether acetate was used so that the total solid content of the colored resin composition was 15.0% by mass.

<Evaluation of color characteristics>
The colored resin composition immediately after preparation was applied by spin coating onto a 50 mm square, 0.5 mm thick glass substrate (AN100, manufactured by AGC). The rotation speed was adjusted so that the film thickness after heat curing treatment would be 2.0 um.
Each coating film was prebaked at 100°C for 120 seconds. Then, exposure treatment was performed with a 2kW high pressure mercury lamp at an exposure dose of 40mJ/ ^cm2 . Then, heat curing treatment was performed at 230°C for 20 minutes to prepare a substrate. The transmission spectrum of the obtained colored substrate was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd.

<Evaluation of Pattern Formability>
The colored resin composition immediately after preparation was applied by spin coating onto a glass substrate (AN100, manufactured by AGC) having a size of 50 mm square and a thickness of 0.5 mm. The rotation speed was adjusted so that the film thickness after heat curing treatment would be 2.0 μm.
Each coating film was prebaked at 100°C for 120 seconds. Then, exposure processing was performed through an exposure mask having a linear coating portion of 50 μm with an exposure amount of 40 mJ/ ^cm2 by a 2 kW high pressure mercury lamp. Then, development processing was performed for 60 seconds at a developer temperature of 23°C using a 0.04 mass% potassium hydroxide aqueous solution. Then, spray water washing processing was performed for 10 seconds at a water pressure of 1 kg/ ^cm2 . Then, heat curing processing was performed for 20 minutes at 230°C to prepare a pattern substrate A. For the obtained pattern substrate A, the line width (μm) of three linear portions of the pattern was measured using an optical microscope, and the average was calculated. The calculated line width was taken as the line width immediately after preparation.
The line width (μm) of the straight line portion of the pattern was measured in the same manner as above using each of the colored resin compositions stored at 5° C. for 15 days and 30 days after preparation. The measured line widths were defined as the line width 15 days after preparation and the line width 30 days after preparation, respectively, and the line width change in the case of storage for 15 days ((line width 15 days after preparation)−(line width immediately after preparation)) and the line width change in the case of storage for 30 days ((line width 30 days after preparation)−(line width immediately after preparation)) were calculated.

As is clear from Table 3, in the colored resin composition using a colorant-containing liquid containing phthalocyanine compound (1) as in Comparative Example A1, when stored for 15 days after preparation, a significant decrease in the line width of the straight line portion of the pattern is observed compared to immediately after preparation, compared to the colored resin composition using a colorant-containing liquid containing C.I. Pigment Green 58 (pigment) as in Comparative Example A3 and C.I. Pigment Green 59 (pigment) as in Comparative Example A4.

As is clear from Table 5, in the colored resin composition containing phthalocyanine compound (1) as in Comparative Example B1, when stored for 15 days after preparation, a significant decrease in the line width of the straight line portion of the pattern is observed compared to immediately after preparation, compared to the colored resin composition containing C.I. Pigment Green 58 (pigment) in Comparative Example B2 and C.I. Pigment Green 59 (pigment) in Comparative Example B3.

Comparing Examples A1 to A4 and Comparative Example A2 in Table 3, in addition to phthalocyanine compound (1), a compound represented by formula (3) was also included in colorant-containing liquids 1 to 4, which contain 0.05 to 10 parts by mass of the compound represented by formula (3) per 100 parts by mass of phthalocyanine compound (1). In these colored resin compositions, even when stored for 15 or 30 days after preparation, there is almost no reduction in the line width of the straight line portions of the pattern.

As shown in Examples B1 to B7 in Table 4, in the colored resin composition containing 0.80 mass% or less of the compound represented by formula (3) in addition to the phthalocyanine compound (1), almost no decrease in the line width of the straight line portion of the pattern is observed even when stored for 15 or 30 days after preparation.

Even when a compound represented by formula (3) other than compound A was used as in Examples A5 to A12 in Table 3, in the case of colorant-containing liquids 5 to 12, in which a colorant-containing liquid containing 0.05 parts by mass or more and 10 parts by mass or less of a compound represented by formula (3) per 100 parts by mass of phthalocyanine compound (1) was used, almost no reduction in the line width of the straight line portion of the pattern was observed.
Also, when other compounds represented by formula (3) were used, such as in Examples B8 to B11 in Table 4, almost no reduction in the line width of the straight line portion of the pattern was observed.
The reason for this is believed to be that the inclusion of the compound represented by formula (3) suppresses the interaction between the phthalocyanine compound (1) and the photopolymerization initiator, thereby making it possible to suppress a decrease in the polymerization ability and film-curing ability of the photopolymerization initiator due to the interaction between the phthalocyanine compound (1) and the photopolymerization initiator.

Also, as in Examples B12 to B16 in Table 5, even when photopolymerization initiators other than carbazole ketoximes, such as carbazole oximes, indoles, or diphenyl sulfides, are used, there is almost no reduction in the line width of the straight line portions of the pattern when a certain amount of the compound represented by formula (3) is included.

In addition, as in Example B17 in Table 5, even when a different type of alkali-soluble resin is used, it was confirmed that there is almost no reduction in the line width of the straight line portions of the pattern when a certain amount of the compound represented by formula (3) is included.

As is clear from a comparison between Example C1 and Comparative Example C2 in Table 6, it was confirmed that when the compound represented by general formula (3) was used, no decrease in LY was observed compared to when the compound represented by general formula (3) was not used.
Furthermore, as is clear from a comparison between Comparative Example C2 and Comparative Example C3, it was confirmed that when the phthalocyanine compound having the chemical structure represented by general formula (1) was used, LY was clearly improved compared to when a green pigment was used.

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 present 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

A colorant-containing liquid containing (A) a colorant, (B) a solvent, and a compound represented by the following general formula (3) and/or a benzoquinone-based compound,
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1):
a total content of a compound represented by the following general formula (3) and a benzoquinone-based compound is 0.05 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the phthalocyanine compound:

(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 fluorine atom or 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 (3), R a , R b , R c , R d , and R f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)
The colorant-containing liquid according to claim 1, wherein the content of the phthalocyanine compound is 50% by mass or more and 99.5% by mass or less based on the total solid content of the colorant-containing liquid.
The colorant-containing liquid according to claim 1, further comprising (E) a dispersant.
The colorant-containing liquid according to claim 3, wherein the content ratio of the (A) colorant to the (E) dispersant ((A) colorant/(E) dispersant) by mass is 10 or more.
A colored resin composition comprising the colorant-containing liquid according to claim 1, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
The colored resin composition according to claim 5, wherein the total content of the compound represented by formula (3) and the benzoquinone-based compound is 30 parts by mass or less per 100 parts by mass of the (D) photopolymerization initiator.
The colored resin composition according to claim 5, wherein the colorant (A) contains other colorants in addition to the phthalocyanine compound.
A color filter having pixels made using the colored resin composition according to claim 5.
An image display device having the color filter according to claim 8.
A colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound represented by the following general formula (3) and/or a benzoquinone-based compound,
The colored resin composition, wherein the colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (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 fluorine atom, and at least one of A 1 to A 16 represents a group represented by the following general formula (2).)

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

(In formula (3), R a , R b , R c , R d , and R f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)
The colored resin composition according to claim 10, wherein the total content of the compound represented by formula (3) and the benzoquinone-based compound is 0.001 mass% or more in the total solid content of the colored resin composition.
The colored resin composition according to claim 10, wherein the total content of the compound represented by formula (3) and the benzoquinone-based compound is 0.02 mass% or more in the total solid content of the colored resin composition.
The colored resin composition according to claim 10, wherein the total content of the compound represented by formula (3) and the benzoquinone-based compound is 0.80 mass% or less in the total solid content of the colored resin composition.
The colored resin composition according to claim 10, wherein the content of the phthalocyanine compound is 5% by mass or more and 80% by mass or less of the total solid content of the colored resin composition.
The colored resin composition according to claim 10, wherein the total content of the compound represented by formula (3) and the benzoquinone-based compound is 20 parts by mass or less per 100 parts by mass of the (D) photopolymerization initiator.
The colored resin composition according to claim 10, wherein the colorant (A) contains other colorants in addition to the phthalocyanine compound.
A color filter having pixels made using the colored resin composition according to any one of claims 10 to 16.
An image display device having the color filter according to claim 17.
A method for producing a colored resin composition comprising (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, (D) a photopolymerization initiator, and a compound represented by the following general formula (3) and/or a benzoquinone-based compound,
The colorant (A) is a phthalocyanine compound having a chemical structure represented by the following general formula (1):
In the production of a colored resin composition, the phthalocyanine compound is mixed with a compound represented by the following general formula (3) and/or a benzoquinone-based compound before mixing the phthalocyanine compound with the (D) photopolymerization initiator:

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

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

(In formula (3), R a , R b , R c , R d , and R f each independently represent a hydrogen atom, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, and R e represents a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms.)
The method for producing a colored resin composition according to claim 19, wherein the total amount of the compound represented by formula (3) and the benzoquinone-based compound is 0.001 mass% or more of the total solid content of the colored resin composition.
The method for producing a colored resin composition according to claim 19, wherein the total amount of the compound represented by formula (3) and the benzoquinone-based compound is 0.02 mass% or more of the total solid content of the colored resin composition.
The method for producing a colored resin composition according to claim 19, wherein the total amount of the compound represented by formula (3) and the benzoquinone-based compound is 0.80 mass% or less of the total solid content of the colored resin composition.