JP2020170079A - Colored resin composition, color filter, and image display device - Google Patents

Abstract

To provide a colored resin composition capable of forming a pattern having practically sufficient contrast and luminance.SOLUTION: The colored resin composition contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator. The colorant (A) contains a specific zinc phthalocyanine compound having one or more groups represented by formula (2). The photopolymerization initiator (D) contains a photopolymerization initiator (d1) having a fluorene skeleton. (In the formula (2), X represents a divalent linking group; a benzene ring in the formula (2) may have an arbitrary substituent; and * represents a bond.)SELECTED DRAWING: None

Description

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

Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for manufacturing a color filter used in a liquid crystal display device or the like. Among them, the pigment dispersion method having excellent characteristics on average is most widely adopted from the viewpoints of spectral characteristics, durability, pattern shape, accuracy and the like.

In recent years, color filters are required to have higher brightness, higher contrast, and higher color gamut. Pigments are generally used as the color material that determines the color of the color filter from the viewpoint of heat resistance, light resistance, etc. However, pigments are no longer able to meet market demands especially for high brightness, and colors. There is a lot of study on using dyes instead of pigments as materials. For green pixels, studies have been conducted on using a specific phthalocyanine compound as a dye (see, for example, Patent Documents 1 and 2).

Japanese Unexamined Patent Publication No. 2014-043556 Japanese Unexamined Patent Publication No. 2015-072440

As a result of studies by the present inventors, it was found that the contrast of the obtained color filter is not practically sufficient in the colored resin composition described in Patent Document 1. On the other hand, it has been found that the brightness of the obtained color filter is not practically sufficient in the colored resin composition described in Patent Document 2.
Therefore, an object of the present invention is to provide a colored resin composition capable of forming a pattern having practically sufficient contrast and brightness.

As a result of diligent studies by the present inventors, it has been found that the above problems can be solved by using a specific phthalocyanine compound as a colorant and further using a specific photopolymerization initiator as a photopolymerization initiator. , The present invention has been reached.
That is, the present invention has the following configurations [1] to [5].

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

(In the formula (1), A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, one or more of A ^{1 to} A ¹⁶ Represents a fluorine atom, and one or more of A ^{1 to} A ¹⁶ represents a group represented by the following general formula (2).)

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

[2] The colored resin composition according to [1], wherein the content ratio of the phthalocyanine compound having the chemical structure represented by the general formula (1) is 5% by mass or more in the total solid content.

[3] The colored resin composition according to [1] or [2], wherein the photopolymerization initiator (d1) contains a photopolymerization initiator represented by the following general formula (I).

In formula (I), R ^d1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents any monovalent substituent. q represents an integer from 0 to 3.
R ^d4 and R ^d5 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ^d4 and R ^d5 may be coupled to each other to form a ring. )

[4] A color filter having pixels created by using the colored resin composition according to any one of [1] to [3].
[5] An image display device having the color filter according to [4].

According to the present invention, it is possible to provide a colored resin composition capable of forming a pattern having practically sufficient contrast and brightness.

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

In the present invention, the "weight average molecular weight" refers to the polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).
Further, in the present invention, the "total solid content" means all the components other than the solvent in the colored resin composition.
Further, in the present invention, the "amine value" represents an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH. ..
Further, in the present invention, "CI" means a color index.

[1] Components of Colored Resin Composition Each component of the colored resin composition of the present invention will be described below. The colored resin composition according to the present invention contains (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator as essential components, and if necessary, other than the above components. Other additives and the like may be blended.
Hereinafter, each component will be described.

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

In the formula (1), A ^{1 to} A ¹⁶ independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, one or more of A ¹ to A ¹⁶ represents a fluorine atom, and one or more 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 the formula (2) may have an arbitrary substituent. * Represents a bond.

The (A) colorant contained in the colored resin composition of the present invention contains a phthalocyanine compound (1), and the phthalocyanine compound (1) is represented by the π-π interaction between phthalocyanine rings, which is represented by the general formula (2). Molecules are likely to associate with each other due to the π-π interaction between the groups, and the packing of the molecules is tighter due to the presence of fluorine atoms with a small atomic radius, and the brightness is high due to the formation of aggregates between the two molecules. It is considered to be.

On the other hand, the phthalocyanine compound (1) is not limited to the formation of an aggregate between two molecules due to the π-π interaction between the molecules, and further the association proceeds to easily form an aggregate. It is considered that the contrast tends to decrease due to light scattering.

Therefore, in the colored resin composition of the present invention, by containing a photopolymerization initiator having a fluorene skeleton, the π-π interaction between the fluorene skeleton and the phthalocyanine ring causes the phthalocyanine compound (1) to be intermolecularly intermolecular. It is considered that the formation of aggregates in Fluorene is promoted, the formation of aggregates due to excessive association is suppressed, light scattering is less likely to occur, and the decrease in contrast can be suppressed. At this time, it is considered that the aromatic hydrocarbon ring skeleton is more likely to interact with the electron-rich phthalocyanine skeleton than the aromatic heterocyclic skeleton due to the charge transfer action.

(A ^{1 to} A ¹⁶ )
In the above formula (1), A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A ¹ to A ¹⁶ represents a fluorine atom, and one or more 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 the formula (2) may have an arbitrary substituent. * Represents a bond.

(X)
X in the general formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, but is an oxygen atom, a sulfur atom, or a -N (R ^a1 ) ^-group (R ^a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms). Can be mentioned. Among these, an oxygen atom or a sulfur atom is preferable, and an oxygen atom is more preferable, from the viewpoint of stability of the phthalocyanine compound (1) at the time of baking.

(Substituents that the benzene ring may have)
Further, the benzene ring in the formula (2) may have an arbitrary substituent. It is not particularly restricted but includes the substituent, a halogen atom, an alkyl 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, an aryloxy group (-OR ^B group (wherein, R ^B represents an aryl group.)), an aryloxycarbonyl group (-COOR ^B group (wherein, R ^B is aryl represents a group.)), with alkyl groups contained in these groups (-R ^a group) and an aryl group (-R ^B group), may be further substituted by these substituents. Among these, an alkoxycarbonyl group is preferable from the viewpoint of solubility in a solvent and brightness.

The alkyl group contained in these groups may be linear, branched or cyclic, but is preferably linear from the viewpoint of solubility in a solvent and brightness.
The number of carbon atoms of the alkyl group is not particularly limited, but usually 1 or more and 2 or more is preferable, 6 or less is preferable, 5 or less is more preferable, and 4 or less is further preferable. When it is at least the above lower limit value, lipophilicity is improved and the solubility of the phthalocyanine compound (1) in a solvent tends to be improved, and when it is at least the above upper limit value, π- between phthalocyanine rings It does not inhibit π interaction and tends to increase brightness due to the formation of aggregates between two molecules.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and a methyl group or an ethyl group is preferable from the viewpoint of solubility in a solvent and brightness, and an ethyl group is preferable. Is more preferable.

Further, 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 preferably 4 or more and 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is at least the above lower limit value, the solubility of the phthalocyanine compound (1) in a solvent tends to be improved, and when it is at least the above upper limit value, the hue change due to the aryl group tends to be suppressed.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic 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, a heptalene ring, and the like having one free valence.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, and an isooxazole having one free valence. Ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, frazan ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene Ring, 2-benzothiophene ring, 1H-pyrrolidin ring, indole ring, isoindole ring, indridin ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinolin ring, 4H-quinolidine ring, benzo Examples include groups such as an imidazole ring, a 1H-indazole ring, a quinoxazole ring, a quinazoline ring, a synnoline ring, a phthalazine ring, a 1,8-naphthylidine ring, a purine ring, and a pteridine ring.

When the benzene ring in the formula (2) has an arbitrary substituent, the number of substitutions is not particularly limited, but the lipophilicity that affects the solubility of the phthalocyanine compound (1) in the solvent and the lipophilicity of the phthalocyanine compound (1) From the viewpoint of improving brightness by forming an aggregate between two molecules, the number of substitutions is preferably 1 for each benzene ring.
When the benzene ring in the formula (2) has an arbitrary substituent, the substitution position may be the o-position, the m-position, or the p-position, but the phthalocyanine compound derived from the symmetry of the molecule. From the viewpoint of improving brightness by forming an aggregate between the two molecules in (1), the p-position is preferable.

One or more of A ^{1 to} A ¹⁶ represent fluorine atoms, but one or more of A ^{1 to} A ⁴ are fluorine atoms from the viewpoint of improving brightness by forming an aggregate between two molecules of the phthalocyanine compound (1). At least one of A ^{5 to} A ⁸ is a fluorine atom, one or more of A ^{9 to} A ¹² is a fluorine atom, and one or more of A ^{13 to} A ¹⁶ is a fluorine atom. Two or more of A ^{1 to} A ⁴ are fluorine atoms, two or more of A ^{5 to} A ⁸ are fluorine atoms, and two or more of A ^{9 to} A ¹² are fluorine. It is more preferable that the atom is an atom and two or more of A ^{13 to} A ¹⁶ are fluorine atoms.

Further, one or more of A ^{1 to} A ¹⁶ represents a group represented by the general formula (2), but from the viewpoint of solubility in a solvent, one or more of A ^{1 to} A ⁴ is the general. It is a group represented by the formula (2), one or more of A ^{5 to} A ⁸ is a group represented by the general formula (2), and one or more of A ^{9 to} A ¹² is the general. It is preferable that the group is represented by the formula (2) and one or more of A ^{13 to} A ¹⁶ is a group represented by the general formula (2), and 2 of A ^{1 to} A ⁴ One or more are groups represented by the general formula (2), and two or more of A ^{5 to} A ⁸ are groups represented by the general formula (2), and 2 of A ^{9 to} A ¹² It is more preferable that one or more are the groups represented by the general formula (2), and two or more of A ^{13 to} A ¹⁶ are the groups represented by the general formula (2).
In particular, from the viewpoints of color, brightness, and solubility in a solvent required by a color filter, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ , and A ¹⁵ are the general formulas (2). It is particularly preferable that the group represented by) and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ and A ¹⁶ are fluorine atoms.

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

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

The colorant (A) may contain other colorants in addition to the phthalocyanine compound (1). Examples of other colorants include pigments and dyes. Among these, when used for green pixel applications, it is preferable to use green pigments, green dyes, yellow pigments, yellow dyes and the like.
Examples of the green pigment include C.I. I. Pigment Green 7, 36, 58, 59, 62, 63 and the like, from the viewpoint of brightness, C.I. I. Pigment Green 58 is preferred.
Among those classified as dyes by the color index, C.I. I. As a solvent dye, C.I. I. Solvent Greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and C.I. I. As an acid dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Mordant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like. Among these, from the viewpoint of suppressing dye decomposition during heat firing, C.I. I. Solvent greens 1, 3, 4, 5, 7, 28, 29, 32, 33, 34 and 35 are preferred.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 125, 126, 127, 127: 1, 128, 129, 133, 134, 136, 137, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and other compounds in a 1: 1 complex of azobarbituric acid represented by the following formula (i) with nickel or a tautomer thereof. (Hereinafter, it may be referred to as a “nickel azo complex represented by the formula (i)”) or the like in which is inserted.

In addition, examples of the other compound include compounds represented by the following formula (ii).

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

Examples of the yellow dye include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include specific compounds described in JP-A-2010-168531.
Among those classified as dyes by the color index, C.I. I. As a solvent dye, C.I. I. Examples include Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, 163 and the like. Also, C.I. I. As an acid dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184. , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and their derivatives. Can be mentioned. Also, C.I. I. As a direct dye, C.I. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 Dyes such as 136, 138 and 141 can be mentioned. In addition, C.I. I. As a modern dye, C.I. I. Dyes such as Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65 can be mentioned, preferably C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. I. Acid Yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184. , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251, 23, 25. , 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and derivatives thereof.
Among these, from the viewpoint of suppressing dye decomposition during heat firing, C.I. I. It is preferably at least one selected from the group consisting of Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162 and 163.

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

The content ratio of the (A) colorant in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass in the total solid content of the colored resin composition. The above is further preferable, 30% by mass or more is further preferable, 35% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 45% by mass or less is preferable. Especially preferable. When it is at least the lower limit value, color characteristics such as brightness and color gamut tend to be improved, and when it is at least the upper limit value, pattern formability tends to be good.

The content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, and 10% by mass in the total solid content of the colored resin composition. The above is further preferable, 15% by mass or more is further preferable, 20% by mass or more is particularly preferable, 45% by mass or less is more preferable, 40% by mass or less is more preferable, 35% by mass or less is further preferable, and 30% by mass or less is more preferable. Even more preferably, 25% by mass or less is particularly preferable. When it is at least the lower limit value, color characteristics such as brightness and color gamut tend to be improved, and when it is at least the upper limit value, pattern formability tends to be good.

When other colorants are contained, the content ratio thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more in the total solid content of the colored resin composition. Preferably, 5% by mass or more is more preferable, 10% by mass or more is particularly preferable, 40% by mass or less is more preferable, 35% by mass or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less is particularly preferable. When it is at least the lower limit value, color characteristics such as brightness and color gamut tend to be improved, and when it is at least the upper limit value, pattern formability tends to be good.

[1-2] (B) Solvent The (B) solvent dissolves or disperses a colorant, an alkali-soluble resin, a photopolymerization initiator, and other components in the colored resin composition and pigment dispersion of the present invention, and has a viscosity. Has the function of adjusting.
The solvent (B) may be any solvent that can dissolve or disperse each component.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol mono-n-butyl ether. Propropylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl Glycol monoalkyl ethers such as -3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether;

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

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

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methylisobutyrate, ethylene glycol acetate, ethyl propionate, propylpropionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

Commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2. Solvento # 150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, jiglime (all trade names) and the like. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

When forming the pixels of the color filter by the photolithography method, select a solvent having a boiling point in the range of 100 to 200 ° C. (under the condition of pressure 1013.25 [hPa]. Hereinafter, the boiling points are all the same). Is preferable. More preferably, it has a boiling point of 120 to 170 ° C.
Glycolalkyl ether acetates are preferable because they have a good balance of coatability and surface tension in the solvent and the solubility of the constituent components in the composition is relatively high.

Further, the glycol alkyl ether acetates may be used alone or in combination with other solvents. Glycol monoalkyl ethers are particularly preferable as the solvent to be used in combination. Of these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of the constituent components in the composition. The glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained later tends to increase and the storage stability tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. By using such a solvent having a high boiling point in combination, the colored resin composition becomes difficult to dry, but there is an effect that it is difficult to break the mutual relationship of the pigment dispersion liquid due to rapid drying. The content ratio of the high boiling point 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 with respect to the solvent (B). By setting it to the above lower limit value or more, for example, it tends to be easy to prevent color material components and the like from precipitation and solidifying at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the composition It tends to be easy to avoid slowing down the drying rate and causing problems such as poor tact in the vacuum drying process and pin marks on the prebake.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher.
As a preferable high boiling solvent, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanoldi Examples include acetate and triacetin.

When forming the pixels of a color filter by an inkjet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is suitable. When it is at least the above lower limit value, the uniformity of the obtained coating film tends to be good, and when it is at least the above upper limit value, the residual solvent during firing tends to be easily reduced.
Further, from the viewpoint of the uniformity of the obtained 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 the manufacture of color filters by the inkjet method, the ink emitted from the nozzle is extremely fine, ranging from several to several tens of pL, so the solvent evaporates and the ink concentrates before landing around the nozzle opening or in the pixel bank.・ Tends to dry. In order to avoid this, the boiling point of the solvent is preferably high, and specifically, it is preferable to contain a solvent having a boiling point of 180 ° C. or higher. It contains a solvent having a boiling point of 200 ° C. or higher, more preferably 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more in the total solvent contained in the colored resin composition. By setting the value to the lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.

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

On the other hand, if the solvent contains alcohols, the ejection stability in the inkjet method may deteriorate. Therefore, the alcohol content is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less in the total solvent.

The content ratio of the solvent in the colored resin composition of the present invention is not particularly limited, but the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. When the value is not more than the upper limit, the coating film tends to be easily formed. On the other hand, the lower limit of the solvent content ratio is usually 70% by mass or more, preferably 75% by mass or more, and more preferably 78% by mass or more in consideration of viscosity suitable for coating.

[1-3] (C) Alkali-soluble resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing the alkali-soluble resin (C), it is possible to achieve both film curability by photopolymerization and solubility by a developing solution.
Examples of the alkali-soluble resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, and JP-A-11-174224. Known polymer compounds described in JP-A-2000-563118, JP-A-2003-233179, etc. can be used, but the following (C-1) to (C-) are preferable. Examples thereof include the resin of 5).
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy groups of the copolymer. It may be referred to as an alkali-soluble resin (hereinafter referred to as "resin (C-1)") obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction. )
(C-2) A linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter, may be referred to as "resin (C-2)").
(C-3) A resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin (C-2) (hereinafter, may be referred to as "resin (C-3)").
(C-4) (Meta) acrylic resin (hereinafter, may be referred to as "resin (C-4)")
(C-5) Epoxy (meth) acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (C-5)")
Of these, resin (C-1) is particularly preferable, and will be described in detail below.

The resins (C-2) to (C-5) may be any resin as long as they are dissolved by an alkaline developer and have enough solubility to carry out the desired developing treatment. Those described as the same item in Japanese Patent Application Laid-Open No. 2009-025813 can be preferably adopted.

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

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

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

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

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

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

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

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

In the copolymer of the epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the content ratio of the repeating unit derived from the mono (meth) acrylate represented by the general formula (VI) is as described above. Among the repeating units derived from other radically polymerizable monomers, those containing 5 to 90 mol% are preferable, those containing 10 to 70 mol% are more preferable, and those containing 15 to 50 mol% are particularly preferable. ..

The radically polymerizable monomer other than the mono (meth) acrylate represented by the general formula (VI) is not particularly limited, but specifically, for example, styrene or styrene. Vinyl aromatics such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene; (meth) acrylic acid Methyl, ethyl (meth) acrylate, -n-propyl (meth) acrylate, -iso-propyl (meth) acrylate, -n-butyl (meth) acrylate, -sec-butyl (meth) acrylate, ( Meta) Acrylic acid-tert-butyl, (Meta) Pentyl acrylate, (Meta) Neopentyl acrylate, (Meta) Isoamyl acrylate, (Meta) hexyl acrylate, (Meta) -2-ethylhexyl acrylate, (Meta) Lauryl acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, -2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobolonyl (meth) acrylate, Adamanthyl (meth) acrylate, propagil (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate , (Meta) salicyl acrylate, (meth) acrylate frill, (meth) acrylate flufuryl, (meth) acrylate tetrahydrofuryl, (meth) acrylate pyranyl, (meth) acrylate benzyl, (meth) acrylate phenethyl , (Meta) cresyl acrylate, (meth) acrylate-1,1,1-trifluoroethyl, (meth) perfluoroethyl acrylate, (meth) perfluoro-n-propyl acrylate, (meth) acrylic Perfluoro-iso-propyl acid, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, -2-hydroxy (meth) acrylate (Meta) acrylic acid esters such as ethyl, (meth) acrylic acid-2-hydroxypropyl; (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N- Diethylamide, (meth) acrylic acid N, N-dipropylamide, (me (T) (Meta) acrylic acid amides such as N, N-di-iso-propylamides and (meth) acrylic acid anthracenylamides; (meth) acrylic acid anilides, (meth) acryloylnitrile, achlorine, vinyl chloride. , Vinyl compounds such as vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itacone. Kind: Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide; N- (meth) acryloylphthalimide and the like.

Among these other radically polymerizable monomers, it is selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide from the viewpoint of imparting excellent heat resistance and strength to the colored resin composition1. It preferably contains more than a seed. In particular, among the repeating units derived from other radically polymerizable monomers, the content ratio of the repeating units derived from one or more selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleimide is 1 to 1. It is preferably 70 mol%, more preferably 3 to 50 mol%.

A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; and diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; Propropylene glycol monoalkyl ether acetates; Acetate esters such as dipropylene glycol monoalkyl ether acetates; Ethylene glycol dialkyl ethers; Diethylene glycol dialkyl ethers such as methylcarbitol, ethylcarbitol, butylcarbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; benzene, toluene, xylene, octane, Hydrocarbons such as decane; Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate; dimethylformamide, N-methylpyrrolidone and the like. Be done. These solvents may be used alone or in combination of two or more.

The amount of these solvents used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the obtained copolymer. By keeping the amount of the solvent used within the above range, it tends to be easy 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 a commonly used organic peroxide catalyst or azo compound catalyst should be used. Can be done. Examples of the organic peroxide catalyst include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates.

Specific examples thereof include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-butylperoxy-2-ethyl. Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (T-Butyl Peroxy) Hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl peroxide, dicumylhydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) par Oxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane , 1,1-Bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane and the like.

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

The copolymerization reaction may be carried out by dissolving the monomer used in the copolymerization reaction and the radical polymerization initiator in a solvent and raising the temperature with stirring, or a monomer to which the radical polymerization initiator is added. , The temperature may be raised, and the mixture may be added dropwise to the stirred solvent. Alternatively, the monomer may be dropped while the temperature is raised by adding a radical polymerization initiator to the solvent. The reaction conditions can be freely changed according to the target molecular weight.

In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth) acrylate, and the like. It is preferably composed of 10 to 95 mol% of the repeating unit derived from the radically polymerizable monomer of the above, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 30 to 20 of the former. Those consisting of 70 mol% and the latter 70 to 30 mol% are particularly preferable.

By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth) acrylate to the above lower limit value or more, the addition amount of unsaturated monobasic acid or polybasic acid anhydride described later tends to be sufficient, while Therefore, by setting the content ratio of the repeating unit derived from another radically polymerizable monomer to the above lower limit value or more, the heat resistance and strength tend to be sufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali) are added to the epoxy group portion of the copolymer of the epoxy resin-containing (meth) acrylate and another radically polymerizable monomer. React with soluble component).

As the unsaturated monobasic acid to be added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.
Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. One of these may be used alone, or two or more thereof may be used in combination.

By adding such a component, the resin (C-1) can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy groups of the copolymer, but preferably to 30 to 100 mol%, more preferably to 50 to 100 mol%. By setting the value to the lower limit or more, the stability of the colored resin composition with time tends to be improved. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, as the polybasic acid anhydride added to the hydroxyl group generated when the unsaturated monobasic acid is added to the epoxy group of the copolymer, known ones can be used.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone. Examples thereof include anhydrides of acids having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, tetrahydrophthalic anhydride and / or succinic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the resin (C-1).
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30-80 mol%. When it is set to the upper limit value or less, the residual film ratio during development tends to be good, and when it is set to the lower limit value or more, the solubility tends to be sufficient. As a method for adding the polybasic acid anhydride to the hydroxyl group, a known method can be adopted.

Further, in order to improve the photosensitivity, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. You may.
Further, in order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the generated carboxyl groups.

Further, both of them may be added.
Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group and an alkyl group. As commercial products, for example, the product names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", "Denacol EX-146" manufactured by Nagase ChemteX There are "Denacol EX-171", "Denacol EX-192" and the like.

The structure of such a resin is described in, for example, JP-A-8-297366 and JP-A-2001-89533, and is already known.
The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of the resin (C-1) is not particularly limited, but is preferably 3000 to 100000, and particularly preferably 5000 to 50000. When it is at least the above lower limit value, the heat resistance and film strength tend to be good, and when it is at least the above upper limit value, the solubility in a developing solution tends to be good. As a guideline for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

On the other hand, from the viewpoint of coating film curability during ultraviolet exposure, among the (C) alkali-soluble resins, the (c1) acrylic copolymer resin having an ethylenically unsaturated group in the side chain is preferable.
(C1) The partial structure of the acrylic copolymer resin containing the side chain having an ethylenically unsaturated group is not particularly limited, but from the viewpoint of achieving both the coating curability during ultraviolet exposure and the alkali solubility during alkaline development. For example, it is preferable to have a partial structure represented by the following general formula (I).

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

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

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

The polybasic acid residue means a monovalent group obtained by subtracting one OH group from the polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid One or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid and biphenyltetracarboxylic acid can be mentioned.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable from the viewpoint of patterning characteristics. Are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(C1) The content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, preferably 20 mol. % Or more is more preferable, 30 mol% or more is further preferable, 40 mol% or more is further preferable, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, and 95 mol% or less is more preferable, 90 mol. % Or less is more preferable, 85 mol% or less is further preferable, 80 mol% or less is further preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable. When it is at least the above lower limit value, the coating film curability during ultraviolet exposure tends to be improved, and when it is at least the above upper limit value, the alkali solubility at the time of alkaline development tends to be improved.

(C1) The content ratio of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more. 20 mol% or more is more preferable, 30 mol% or more is further preferable, 40 mol% or more is further preferable, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, and 95 mol% or less is preferable. 90 mol% or less is more preferable, 85 mol% or less is further preferable, 80 mol% or less is further preferable, 75 mol% or less is particularly preferable, and 70 mol% or less is most preferable. When it is at least the above lower limit value, the coating film curability during ultraviolet exposure tends to be improved, and when it is at least the above upper limit value, the alkali solubility at the time of alkaline development tends to be improved.

(C1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains a partial structure represented by the general formula (I), the other partial structure is not particularly limited, but is used during alkaline development. From the viewpoint of alkali solubility, for example, it is also preferable to have a partial structure represented by the following general formula (II).

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

(R ⁴ )
In the formula (II), R ⁴ represents an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, or an alkenyl group which may have a substituent. ..
Examples of the alkyl group in R ⁴ include a linear, branched chain or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less. It is more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of developability.
The substituents 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 and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the aromatic ring group in R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or a pyrene. Examples thereof include groups such as a ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyroloymidazole ring, pyrrolopyrazole ring, pyrolopyrrole ring, thienopyrol ring, thienothiophene ring, flopyrol ring, flofuran ring, thienofran ring, benzoisooxazole ring, benzoiso Thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridin ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring And so on. Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable.
The substituents 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 and an epoxy group. , Oligoethylene glycol group, phenyl group, carboxyl group and the like, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

Examples of the alkenyl group in R ⁴ include linear, branched chain or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less is particularly preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkenyl group include vinyl group, allyl group, 2-propen-2-yl group, 2-butene-1-yl group, 3-butene-1-yl group, 2-pentene-1-yl group, and the like. Examples thereof include 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl and the like. Among these, a vinyl group or an allyl group is preferable, and a vinyl group is more preferable, from the viewpoint of developability.

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 carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

As described above, 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. Among them, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability and film strength.

The content ratio of the partial structure represented by the general formula (II) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain (c1) is not particularly limited, but is preferably 1 mol% or more, and 5 mol% or more. Is more preferable, 10 mol% or more is further preferable, 20 mol% or more is particularly preferable, 70 mol% or less is preferable, 60 mol% or less is more preferable, 50 mol% or less is further preferable, and 40 mol% or less is preferable. Especially preferable. When it is at least the above lower limit value, the alkali solubility tends to be improved, and when it is at least the above upper limit value, the storage stability of the colored resin composition tends to be improved.

(C1) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), the phthalocyanine compound (1) and the acrylic copolymer resin have an improved affinity as the other partial structure contained therein. From the viewpoint of alkali solubility of the phthalocyanine compound (1), it is preferable that the partial structure represented by the following general formula (III) is contained.

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. Represents an alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent. t represents an integer from 0 to 5.

(R ⁶ )
In the above formula (III), R ⁶ is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, or a carboxyl group. , Halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples of the alkyl group in R ⁶ include a linear, branched chain or cyclic alkyl group. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, and more preferably 18 or less. It is more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. Among these, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable, from the viewpoint of heat resistance.
The substituents 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 and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkenyl group in R ⁶ include a linear, branched chain or cyclic alkenyl group. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less is particularly preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkenyl group include vinyl group, allyl group, 2-propen-2-yl group, 2-butene-1-yl group, 3-butene-1-yl group, 2-pentene-1-yl group, and the like. Examples thereof include 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl and the like. Among these, a vinyl group or an allyl group is preferable, and a vinyl group is more preferable, from the viewpoint of exposure sensitivity at the time of ultraviolet exposure.

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 carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the alkynyl group in R ⁶ include a linear, branched or cyclic alkynyl group. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less is particularly preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkynyl group include 1-propyne-3-yl group, 1-butyne-4-yl group, 1-pentyne-5-yl group, 2-methyl-3-butin-2-yl group, 1, Examples thereof include 4-pentadiine-3-yl group, 1,3-pentadiine-5-yl group, 1-hexin-6-yl group, and the like.

The substituents 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 carboxyl group. From the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is preferable from the viewpoint of storage stability of the acrylic copolymer resin.

Examples of the alkoxy group in R ⁶ include linear, branched or cyclic alkoxy groups. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and the like.

The substituents 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 and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkyl sulfide group in R ⁶ include a linear, branched chain or cyclic alkyl sulfide group. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When it is at least the above lower limit value, lipophilicity tends to be improved and solubility in a solvent tends to be improved, and when it is at least the above upper limit value, hydrophilicity is improved and alkali solubility tends to be improved. is there.

Specific examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group and the like. Among these, a methyl sulfide group or an ethyl sulfide group is preferable from the viewpoint of developability.

The substituents 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 and a phenyl group. Examples thereof include a group, a carboxyl group, an acryloyl group and a methacryloyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

As described above, R ⁶ has an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, a carboxyl group, and a halogen. It represents an alkylsulfide group which may have an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or a substituent. Among these, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable, from the viewpoint of developability. preferable.

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

(C1) The content ratio of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, and 2 mol% or more. Is more preferable, 5 mol% or more is further preferable, 8 mol% or more is particularly preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, 30 mol% or less is further preferable, and 20 mol% or less is preferable. Especially preferable. When it is at least the above lower limit value, the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin tends to be improved, and the alkali solubility tends to be improved, and when it is at least the above upper limit value, other partial structures are contained. The proportion tends to increase and the alkali solubility tends to improve.

(C1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (I), the other partial structure contained is the following general formula from the viewpoint of developability. It is also preferable to have a partial structure represented by (IV).

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

(C1) The content ratio of the acrylic copolymer resin having an ethylenically unsaturated group in the side chain when it contains the partial structure represented by the general formula (IV) is not particularly limited, but is preferably 5 mol% or more. 10 mol% or more is more preferable, 20 mol% or more is further preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, and 60% mol or less is further preferable. When it is at least the above lower limit value, the alkali solubility tends to be improved, and when it is at least the above upper limit value, the storage stability of the colored resin composition tends to be improved.

On the other hand, 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, further preferably 40 mgKOH / g or more, still more preferably 50 mgKOH / g or more. 60 mgKOH / g or more is particularly preferable, 300 mgKOH / g or less is preferable, 250 mgKOH / g or less is more preferable, 200 mgKOH / g or less is further preferable, and 150 mgKOH / g or less is even more preferable. When it is at least the above lower limit value, the alkali solubility tends to be improved, and when it is at least the above upper limit value, the storage stability of the colored resin composition tends to be improved.

The weight average molecular weight (Mw) of the alkali-soluble resin (C) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, still more preferably 7000 or more, particularly preferably. It is 8000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. When it is at least the above lower limit value, heat resistance and coating film curability tend to be improved, and when it is at least the above upper limit value, alkali solubility tends to be improved.

The content ratio of the (C) alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 5% by mass or more in the total solid content of the colored resin composition. It is 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, particularly preferably 30% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably. It is 50% by mass or less, more preferably 40% by mass or less. By setting the value to the lower limit or more, a strong film can be obtained, and the adhesion to the substrate tends to be excellent. Further, when the value is not more than the upper limit value, the permeability of the developing solution to the exposed portion is low, and there is a tendency that deterioration of the surface smoothness and sensitivity of the pixel can be suppressed.

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

The (D) photopolymerization initiator in the colored resin composition of the present invention includes a photopolymerization initiator (d1) having a fluorene skeleton (hereinafter, may be referred to as “photopolymerization initiator (d1)”).
By containing the photopolymerization initiator (d1), the π-π interaction between the fluorene skeleton and the phthalocyanine ring of the phthalocyanine compound (1) suppresses the formation of aggregates of the phthalocyanine compound (1) and causes light scattering. Is less likely to occur, and it is considered that the decrease in contrast can be suppressed.

Among the photopolymerization initiators (d1) having a fluorene skeleton, the photopolymerization initiator represented by the following general formula (I) is preferable from the viewpoint of solubility in a solvent and suppression of contrast decrease.

In formula (I), R ^d1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents any monovalent substituent. q represents an integer from 0 to 3.
R ^d4 and R ^d5 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ^d4 and R ^d5 may be coupled to each other to form a ring.

(R ^d1 )
In the formula (I), R ^d1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group at R ^d1 may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting the number of carbon atoms of the alkyl group to the above upper limit or less, the solubility in a solvent is improved, and the π-π interaction with the phthalocyanine ring suppresses the formation of aggregates of the phthalocyanine compound (1) and contrasts. Tends to suppress the decline.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group and the like. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferable, a methyl group or an ethyl group is more preferable, and a methyl group is further preferable.
Substituents 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, F, Cl, Br, and I. Examples thereof include halogen atoms and hydroxyl groups such as, and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Moreover, from the viewpoint of sensitivity, it is preferable that it is not substituted.

Examples of the aromatic ring group in R ^d1 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic 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, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

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, F, Cl, Br, and I. Examples thereof include halogen atoms such as, hydroxyl groups and nitro groups, and from the viewpoint of solvent solubility, alkoxy groups or hydroxyl groups having 1 to 3 carbon atoms are preferable.

Among these, from the viewpoint of sensitivity, R ^d1 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group or an ethyl group. It is preferably a methyl group, particularly preferably a methyl group.

(R ^d2 )
In the formula (I), R ^d2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
The alkyl group in R ^d2 may be linear, branched, cyclic, or a bond thereof, but from the viewpoint of solvent solubility, it is preferably linear or branched, and the branched form is more preferable. preferable. On the other hand, from the viewpoint of sensitivity, a group in which a linear alkyl group and a cyclic alkyl group are bonded is preferable.

The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and most preferably 7 or more. Further, it is preferably 12 or less, more preferably 10 or less, still more preferably 9 or less, and particularly preferably 8 or less. When the number of carbon atoms of the alkyl group is at least the above lower limit value, the solvent solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high.

Substituents 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, and an alkoxy group having 1 to 10 carbon atoms. Examples thereof include a carbonyl group, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and the like, and an alkoxy group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility. Moreover, from the viewpoint of sensitivity, it is preferable that it is not substituted.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group and cyclopentylmethyl group. Cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group and the like can be mentioned. Among these, from the viewpoint of solvent solubility, an isopentyl group, a cyclopentyl methyl group, a cyclopentyl ethyl group, or a cyclohexyl ethyl group is preferable, a cyclopentyl ethyl group or a cyclohexyl ethyl group is more preferable, and a cyclohexyl ethyl group is further preferable.

Examples of the aromatic ring group in R ^d2 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic 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, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

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, F, Cl, Br, and I. Examples thereof include halogen atoms such as, hydroxyl groups and nitro groups, and from the viewpoint of solvent solubility, alkoxy groups or hydroxyl groups having 1 to 5 carbon atoms are preferable. The alkyl chain portion of the substituent may be linear or branched, and further has a substituent such as an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a hydroxyl group, or a nitro group. You may be doing it.

Among these, from the viewpoint of solubility in a solvent and suppression of contrast reduction, R ^d2 is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and a methyl group. , Ethyl group, propyl group is more preferable, and methyl group is particularly preferable.

(P)
In the formula (I), p represents 0 or 1. From the viewpoint of sensitivity, p is preferably 0, while from the viewpoint of solvent solubility, p is preferably 1.

(R ^d3 )
In formula (I), R ^d3 represents any monovalent substituent.
As an arbitrary monovalent substituent, an alkyl group having 1 to 10 carbon atoms such as a methyl group and an ethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; F, Cl, Br, I and the like. Halogen atom; acyl group having 1 to 10 carbon atoms; alkyl ester group having 1 to 10 carbon atoms; alkoxycarbonyl group having 1 to 10 carbon atoms; alkyl halide group having 1 to 10 carbon atoms; 4 to 10 carbon atoms Aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; nitro group; CN group; benzoyl group which may have a substituent; tenoyl group which may have a substituent, etc. Can be mentioned. Examples of the substituent that the benzoyl group or the tenoyl group may have include an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and the like, which have a range of 0 to 3. You may. Among these, a nitro group is preferable from the viewpoint of suppressing a decrease in contrast.
In R ^d3 , when q is 2 or more, a plurality of R ^d3s may be bonded to each other to form a ring. The ring may be an aliphatic ring or an aromatic ring.

(Q)
In the formula (I), q represents an integer of 0 to 3. From the viewpoint of radical generation efficiency, it is preferably 0 or 1, and more preferably 1.

(R ^d4 and R ^d5 )
In the formula (I), R ^d4 and R ^d5 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent.

The alkyl group in R ^d4 and R ^d5 may be linear, branched, cyclic, or a bond thereof, but from the viewpoint of sensitivity, linear or branched is preferable, and linear. Is more preferable.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. , More preferably 6 or less, and particularly preferably 4 or less. When the number of carbon atoms of the alkyl group is at least the above lower limit value, the solvent solubility tends to be good, and when it is at least the above upper limit value, the sensitivity tends to be high.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group and 2-ethylhexyl group. And so on. Among these, from the viewpoint of the balance between sensitivity and solvent solubility, an ethyl group, a propyl group, an isopropyl group, or a butyl group is preferable, an ethyl group or a propyl group is more preferable, and an ethyl group is further preferable.
Substituents 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, F, Cl, Br, and I. Examples thereof include halogen atoms and hydroxyl groups such as, and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferable. Moreover, from the viewpoint of sensitivity, it is preferable that it is not substituted.

Examples of the aromatic ring group in R ^d4 and R ^d5 include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When the number of carbon atoms of the aromatic ring group is at least the above lower limit value, the molecule tends to be stable, and when it is at least the above upper limit value, the solvent solubility tends to be good.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic 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, and a triphenylene ring, which have one free atomic value. Examples include groups such as acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free atomic value. Ring, Pyrrolomidazole ring, Pyrrolopyrazole ring, Pyrrolopyrrole ring, Thienopyrol ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Thienofranc ring, Benzisoxazole ring, Benzimidazole ring, Benzimidazole ring, Pyridine ring, Pyrazine ring, Examples thereof include groups such as a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferable, and a benzene ring having one free valence is more preferable.

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, F, Cl, Br, and I. Examples thereof include halogen atoms such as, hydroxyl groups and nitro groups, and from the viewpoint of solvent solubility, alkoxy groups or hydroxyl groups having 1 to 3 carbon atoms are preferable. Moreover, from the viewpoint of sensitivity, it is preferable that it is not substituted.

Further, R ^d4 and R ^d5 may be bonded to each other to form a ring, and the ring may be an aliphatic ring or an aromatic ring.

Among these, from the viewpoint of sensitivity, each of R ^d4 and R ^d5 is preferably an alkyl group which may have a substituent independently, more preferably an unsubstituted alkyl group, and a butyl group. It is more preferable to have.

Examples of commercially available products of the photopolymerization initiator (d1) include SPI-02 and SPI-03 (both manufactured by Samyang). Further, those described in JP-A-2017-223954, those described in JP-A-2018-532851, those described in JP-A-2018-537518, and those described in JP-A-2019-507108 are used. It can also be used.

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

(D) The photopolymerization initiator may further contain another photopolymerization initiator (d2) in addition to the photopolymerization initiator (d1).
Examples of other photopolymerization initiators (d2) include titanosen derivatives containing titanosen compounds described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118. The hexaarylbiimidazole derivative described; N-aryl-α-amino acids such as halomethylated oxadiazole derivative, halomethyl-s-triazine derivative, N-phenylglycine, etc. described in JP-A-10-39503, N-aryl- Radical activators such as α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Oxime esters described in JP-A-2000-80068, JP-A-2006-36750 and the like. Derivatives and the like can be mentioned.

Specifically, for example, as titanium derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro) Pheni-1-yl), Dicyclopentadienyl Titanium Bis (2,3,5,6-Tetrafluoropheni-1-yl), Dicyclopentadienyl Titanium Bis (2,4,6-Trifluorophenyl) 1-yl), Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopenta) Dienyl) Titanium Bis (2,3,4,5,6-pentafluoropheni-1-yl), Di (Methylcyclopentadienyl) Titanium Bis (2,6-difluoropheni-1-yl), Dicyclo Examples thereof include pentadienyl titanium [2,6-di-fluoro-3- (pyro-1-yl) -pheni-1-yl].

Examples of biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole. Dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like can be mentioned.

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[β- (2'-). Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like can be mentioned.

Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-Triazine and the like can be mentioned.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4). -Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo Aet, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- ( Examples thereof include 4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone.

Examples of the oxime ester derivative include JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, and JP-A-2012. Examples thereof include oxime ester compounds described in Japanese Patent Application Laid-Open No. 519191. Among them, from the viewpoint of sensitivity, 4-acetoxyimimino-5-[9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -5-oxopentanoate methyl is also used as a product name, OXE-. 01, OXE-02, OXE-03 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG314 (manufactured by Changzhou Power Co., Ltd.), NCI-831, NCI-930 (manufactured by ADEKA), etc. Can be mentioned as a preferable one.
As the other photopolymerization initiator (d2), one type may be used alone, or two or more types may be used in combination.

One of these (D) photopolymerization initiators may be used alone, or two or more thereof may be mixed and used.

Further, in addition to the (D) photopolymerization initiator, a chain transfer agent may be further used. The chain transfer agent is a compound having a function of receiving a generated radical and transferring the radical to another compound.
As the chain transfer agent, various compounds having the above functions can be used, and examples thereof include mercapto group-containing compounds and carbon tetrachloride, and the chain transfer effect tends to be high. It is more preferable to use a compound having a mercapto group. It is considered that this is because the bond cleavage is likely to occur due to the small SH binding energy, and a hydrogen drawing reaction or a chain transfer reaction is likely to occur. It is effective for improving sensitivity and surface curability.

Examples of the mercapto group-containing compound include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β-. A mercapto group-containing compound having an aromatic ring such as mercaptonaphthalene and 1,4-dimethylmercaptobenzene; hexanedithiol, decandithiol, butanediolbis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol. Bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritoltetrakis (3-Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Butanediolbis (3-Mercaptobutyrate), Ethethyleneglycolbis (3-Mercaptobutyrate), Trimethylol Propanthris (3- Mercaptobutylate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine Examples thereof include aliphatic mercapto group-containing compounds such as −2,4,6 (1H, 3H, 5H) -trione, and a compound having a plurality of mercapto groups is particularly preferable from the viewpoint of surface smoothness.

Of these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and trimethylpropanthris (3-) among the aliphatic mercapto group-containing compounds is preferable. Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutynate) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione is preferred.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferable, and specifically, trimetylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol. Tris (3-mercaptopropionate), trimethylpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5- Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-Mercaptobutyrate) is more preferred.
These can be used alone or in admixture of two or more.

In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the total solid content of the colored resin composition. 5% by mass or more is further preferable, 7% by mass or more is particularly preferable, 20% by mass or less is more preferable, 15% by mass or less is more preferable, 12% by mass or less is further preferable, and 10% by mass or less is particularly preferable. When it is set to the lower limit value or more, the patterning characteristics after development tend to be secured, and when it is set to the upper limit value or less, the decrease in transmittance due to excessive addition of the photopolymerization initiator tends to be suppressed.

In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (d1) is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more in the total solid content of the colored resin composition. 5% by mass or more is further preferable, 7% by mass or more is particularly preferable, 20% by mass or less is more preferable, 15% by mass or less is more preferable, 12% by mass or less is further preferable, and 10% by mass or less is particularly preferable. When it is at least the lower limit value, the decrease in contrast tends to be suppressed, and when it is at least the upper limit value, the decrease in transmittance due to excessive addition of the photopolymerization initiator tends to be suppressed.

[1-5] Other solids The colored resin composition of the present invention may further contain solids other than the above components, if necessary. Examples of such a component include a photopolymerizable monomer, a dispersant, a dispersion aid, and a surfactant.

[1-5-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, (Refered to be "ethyleney compound") is preferable. The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized and cured by the action of a photopolymerization initiator. The monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept containing a dimer, a trimer, and an oligomer in addition to a monomer in a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more. The number is 8 or less, more preferably 7 or less. When it is at least the lower limit value, the sensitivity tends to be high, and when it is at least the upper limit value, the solubility in a solvent tends to be improved.

Examples of the ethylenic compound include unsaturated carboxylic acid, an ester of the monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, and an unsaturated carboxylic acid. Esther, polyisocyanate compound and (meth) acryloyl-containing hydroxy compound obtained by esterification reaction of saturated carboxylic acid with polyvalent carboxylic acid and polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound and aromatic polyhydroxy compound. Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting the above.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethyl propantriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and other acrylic acid esters. Further, the acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester instead of a methacrylic acid moiety, an itaconic acid ester substituted with an itaconic acid moiety, a crotonic acid ester substituted with a crotonic acid moiety, or a maleic acid substituted with a maleic acid moiety. Esters and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound is not necessarily a single substance, but may be a mixture. Typical examples are, for example, 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, acrylic acid, adipic acid and butanediol. And a condensate of glycerin and the like.

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

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate are also useful.
Further, the ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is formed by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. The provided polyfunctional monomer is preferable, and the aliphatic polyhydroxy compound in this ester is pentaerythritol and / or dipentaerythritol.

One of these monomers may be used alone, but since it is difficult to use a single compound in production, two or more of these monomers may be mixed and used. Further, if necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When it is set to the lower limit value or more, the developing and dissolving characteristics tend to be improved, and when it is set to the upper limit value or less, the manufacturing and handling are improved, and the photopolymerization performance, the surface smoothness of the pixel, etc. are improved. It tends to improve the curability. Therefore, when two or more types of polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferable.

In the present invention, the polyfunctional monomer having a more preferable acid group is mainly a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, or dipentaerythritol pentaacrylate commercially available as TO1382 manufactured by Toa Synthetic Co., Ltd. It is a mixture as an ingredient. Other polyfunctional monomers of this polyfunctional monomer can also be used in combination. Further, those described in paragraphs [0056] and [0057] of JP2013-140346A can also be used.

Further, in the present invention, from the viewpoint of improving the chemical resistance of the pixel and the linearity of the edge of the pixel, it is preferable to use the polymerizable monomer described in JP2013-195971A. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the developing time, it is preferable to use the polymerizable monomer described in JP2013-195974A.

When the colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is not particularly limited, but is usually 0% by mass or more, preferably 5% by mass, in the total solid content of the colored resin composition. % Or more, more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. It is more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When it is at least the above lower limit value, the curability of the coating film tends to be high, and when it is at least the above upper limit value, the decrease in alkali developability tends to be suppressed.

[1-5-2] Dispersant, Dispersion Aid When the colored resin composition of the present invention contains a pigment as (A) a colorant, 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 is excellent in dispersion stability over time.
Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. A system dispersant can be mentioned. Specific examples of these dispersants include EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by Big Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Ruble). Examples thereof include those described in Japanese Patent Application Laid-Open No. 2013-119568), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

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

Examples of the functional group containing a nitrogen atom include a 1st to 3rd amino group and a quaternary ammonium base, and from the viewpoint of dispersibility and storage stability, it is preferable to have a 1st to 3rd amino group. It is more preferable to have a group.
The structure of the repeating unit having a tertiary amino group in the block copolymer is not particularly limited, but from the viewpoint of dispersibility and storage stability, the repeating unit represented by the following general formula (1) is preferable. ..

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

The number of carbon atoms of the alkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less. It is preferably 4 or less, and more preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain 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 the above formula (1) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less. It is preferably 8 or less, and more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less. It is preferably 9 or less, and more preferably 9. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group, and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or It is preferably a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

Among these, from the viewpoint of dispersibility, storage stability, electrical reliability, and developability, R ¹ and R ² are preferably alkyl groups which may have independent substituents, and are preferably methyl groups or methyl groups. It is more preferably an ethyl group.

Examples of the substituent that the alkyl group, aralkyl group or aryl group in the above formula (1) may have include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and there is no such group from the viewpoint of ease of synthesis. It is preferably a substitution.

Further, in the above formula (1), the cyclic structure formed by bonding R ¹ and R ² to each other is, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of them. Can be mentioned. The nitrogen-containing heterocycle is preferably one having no aromaticity, and more preferably a saturated ring. Specifically, for example, the following (IV) can be mentioned.

These cyclic structures may further have substituents.

In the above formula (1), divalent Examples of the linking group X, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ¹³ - group, -COOR ¹⁴ - group [ However, R ¹³ and R ¹⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], and the like, preferably −COO-R ¹⁴ -Group.

Further, the content ratio of the repeating unit represented by the formula (1) in the total repeating units of the block copolymer is preferably 1 mol% or more, more preferably 5 mol% or more. It is more preferably 10 mol% or more, further preferably 15 mol% or more, particularly preferably 20% or more, most preferably 25 mol% or more, and 90 mol% or less. It is preferably 70 mol% or less, more preferably 50 mol% or less, and particularly preferably 40 mol% or less. Within the above range, both dispersion stability and high brightness tend to be possible.

Further, the block copolymer preferably has a repeating unit represented by the following formula (2) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.

In the above formula (2), R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an alkyl group which may have a substituent, and R ¹² is a hydrogen atom or a methyl group.
n is an integer of 1 to 20.

The number of carbon atoms of the alkyl group which may have a substituent in R ¹¹ of the above formula (2) is not particularly limited, but is usually 1 or more, preferably 2 or more, and 10 or less. It is preferable, it is more preferably 6 or less, and further preferably 4 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. Examples of the substituent which may be possessed include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and are preferably unsubstituted from the viewpoint of ease of synthesis.

Further, n in the above formula (2) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, from the viewpoint of compatibility and dispersibility with a binder component such as a solvent. More preferably, it is 5 or less.

Further, the content ratio of the repeating unit represented by the formula (2) in all the repeating units of the block copolymer is preferably 1 mol% or more, more preferably 2 mol% or more. It is more preferably 4 mol% or more, more preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. If it is within the above range, it tends to be possible to achieve both compatibility with a binder component such as a solvent and dispersion stability.

Further, the block copolymer preferably has a repeating unit represented by the following formula (3) from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving the dispersion stability.

In the above formula (3), R ⁸ 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. R ⁹ 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 the above formula (3) is not particularly limited, but is usually 1 or more, preferably 1 or more, and 10 or less. It is preferable, and it is more preferable that it is 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and the like, and among these, a methyl group, an ethyl group, a propyl group and a butyl group. It is preferably a group, a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be linear or branched. Further, it may contain 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 R ⁸ of the above formula (3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms of the aralkyl group which may have a substituent in R ⁸ of the above formula (3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and preferably 12 or less. Is more preferable. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropylene group, and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or It is preferably a phenylbutylene group, more preferably a phenylmethylene group or a phenylethylene group.

Among these, 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 may have in R ⁸ include a halogen atom and an alkoxy group. Further, examples of the substituent which the aryl group or the aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group and the like. Further, the chain-like alkyl group represented by R ⁸ includes both a linear chain and a branched chain.

Further, the content ratio of the repeating unit represented by the formula (3) in all the repeating units of the block copolymer is preferably 30 mol% or more, more preferably 40 mol% or more. It is more preferably 50 mol% or more, more preferably 80 mol% or less, and even more preferably 70 mol% or less. Within the above range, both dispersion stability and high brightness tend to be possible.

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

From the viewpoint of further enhancing the dispersibility, it has an A block having a repeating unit represented by the general formula (1) and a B block having no repeating unit represented by the general formula (1). It is preferably a block copolymer. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Further, it is more preferable that the B block has a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3).

Further, a repeating unit other than the repeating unit represented by the general formula (1) may be contained in the A block, and examples of such a repeating unit include the above-mentioned (meth) acrylic acid ester type. Examples include repeating units derived from monomers. The content of the repeating unit other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and the repeating unit is Most preferably, it is not contained in the A block.

A repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) may be contained in the B block, and examples of such repeating units include , Styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide-based such as (meth) acrylamide and N-methylolacrylamide. Monomer; Vinyl acetate; Acrylamide nitrile; Allyl glycidyl ether, Glycidyl crotonate ether; Repeating units derived from monomers such as N-methacryloylmorpholine. The content of the repeating unit represented by the general formula (2) and the repeating unit other than the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably. Although it is 0 to 20 mol%, it is most preferable that such repeating units are not contained in the B block.

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

Further, the amine value of the block copolymer is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of dispersibility and developability. More preferably, it is more preferably 90 mgKOH / g or more, particularly preferably 100 mgKOH / g or more, most preferably 110 mgKOH / g or more, and preferably 150 mgKOH / g or less, 130 mgKOH or less. More preferably, it is / g or less. Here, the amine value represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH.

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, may be referred to as “Mw”). When it is within the above range, the dispersion stability is good, and dry foreign matter tends to be less likely to be generated during coating by the slit nozzle method.

The block copolymer can be produced by a known method, and for example, it can be produced by living-polymerizing a monomer into which each of the above repeating units is introduced. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P. et al. Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K. et al. Ute, et al, Polym. J. 17,977 (1985), 18,1037 (1986), Koichi Right Hand, Koichi Hatada, Polymer Processing, 36,366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Papers, 46,189 (1989), M. Kuroki, T.K. Aida, J. et al. Am. Chem. Soc, 109,4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43,300 (1985), D.M. Y. Sogoh, W. et al. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be adopted.

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 0.5 parts by mass or more, based on 100 parts by mass of the pigment. Is 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less. It is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. Within the above range, it tends to be possible to obtain a colored resin composition having excellent dispersion stability and high brightness.

When the colored resin composition of the present invention contains a pigment, a pigment derivative or the like may be contained as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrone, perylene, perinone, and diketopyrrolop. Derivatives such as pyrrolop-based and dioxazine-based pigments can be mentioned. As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group, etc. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. Further, these substituents may be substituted in a plurality of pigment skeletons, or may be a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindrin pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, and quinacridone pigment sulfonic acid derivatives. Examples thereof include a sulfonic acid derivative of a diketopyrrolopyrrole pigment and a sulfonic acid derivative of a dioxazine pigment.

[1-5-3] Surfactants Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they may adversely affect various properties. It is preferable to use a nonionic surfactant because of its low value. The content ratio 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 further in the total solid content of the colored resin composition. It is preferably used in the range of 0.1% by mass or more, usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

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

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

When the pigment is dispersed, it is preferable to appropriately use a dispersion aid, a dispersion resin, or the like as described above.
When the dispersion treatment is performed using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several mm or zirconia beads. The temperature at the time of the dispersion treatment is usually set in the range of 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the pigment dispersion liquid, the size of the sand grinder device, and the like, and may be appropriately adjusted.

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

When the colorant does not contain a pigment, a colorant, a solvent, an alkali-soluble resin, a photopolymerization initiator, and if necessary, components other than the above can be mixed to obtain a uniform solution. It is preferable to filter the obtained solution with a filter or the like.

[3] Manufacture 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 by using the above-mentioned colored resin composition.

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

For the transparent substrate and the black matrix-forming substrate, in order to improve the surface physical properties such as adhesiveness, corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. are required. May be done. 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 the thin film forming treatment of 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.

[3-2] 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 further forming a pixel image of usually red, green, and blue. Among the red, green, and blue pixels, the colored resin composition is preferably used as a coating liquid for forming green pixels (resist pattern) (hereinafter, may be abbreviated as "green resist"). Coating, heat drying, image exposure, on the resin black matrix forming surface formed on the transparent substrate using the green resist, or on the metal black matrix forming surface formed by using a chromium compound or other light-shielding metal material. Each process of development and thermosetting is performed to form a pixel image.

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, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, a nickel-tungsten alloy, or the like is used, and these may be laminated in a plurality of layers.
These metal light-shielding films are generally formed by an etching method, and after forming a desired pattern in a film shape by a positive photoresist, dicerium ammonium nitrate and perchloric acid and / or nitric acid are added to chromium. A black matrix is formed by using an etching solution mixed with the above, and for other materials, etching with an etching solution suitable for the material, and finally peeling the positive photoresist with a special release agent. be able to.

In this case, first, a thin film of these metals or metal / metal oxides is formed on the transparent substrate by a vapor deposition or sputtering method. Next, after forming a coating film of the colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

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

[3-3] Pixel formation A colored resin composition of one of red, green, and blue is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is placed on the coating film. Pixel images are formed by image exposure, development, and, if necessary, thermosetting or photocuring through a photomask. A color filter image can be formed by performing this operation on each of the three colored resin compositions of red, green, and blue.

The colored resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like. Above all, according to the die coating method, the amount of coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from the above viewpoint.

If the thickness of the coating film is too large, pattern development becomes difficult and it may be difficult to adjust the gap in the liquid crystal cell formation process, while if it is too small, it becomes difficult to increase the pigment concentration, which is desired. Color development may be impossible. 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. The range is as follows.

[3-4] Drying of Coating Film It is preferable to dry the coating film after applying the colored resin composition to the substrate by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is heated again to dry. The conditions for pre-drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying temperature and drying time are selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 ° C. or higher. The temperature is in the range of ° C. or lower, preferably 70 ° C. or lower, and the drying time is usually in the range of 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

The temperature condition for reheating and drying is preferably higher than the pre-drying temperature, specifically, usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130. It is in the range of ℃ or less. The drying time is usually 10 seconds or more, particularly preferably 15 seconds or more, and usually 10 minutes or less, particularly preferably 5 minutes, although it depends on the heating temperature. The higher the drying temperature, the better the adhesiveness to the transparent substrate, but if it is too high, the binder resin may be decomposed to induce thermal polymerization, resulting in poor development. As the drying step of the coating film, a vacuum drying method in which the coating film is dried in the vacuum chamber without raising the temperature may be used.

[3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on a coating film of a colored resin composition and irradiating a light source of ultraviolet rays or visible light through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the above image exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Examples include laser light sources such as an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when irradiating light of a specific wavelength for use.

[3-6] Development Step In the color filter according to the present invention, a coating film using the colored resin composition according to the present invention is subjected to image exposure with the above-mentioned light source, and then a surfactant and an alkaline compound are applied. An image can be formed on a substrate and produced by developing with an aqueous solution containing the mixture. The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di or triethanolamine, mono-di or trimethylamine , Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), organic alkaline such as choline. Examples include compounds. These alkaline compounds may be a mixture of two or more kinds.

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

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used in combination with an aqueous solution.
The conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable. The developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.

[3-7] Thermosetting treatment The color filter after development is subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are usually selected in a temperature range of 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower, and the time is 5 minutes or longer and 60 minutes or shorter. Selected by range. Through these series of steps, the formation of a one-color patterning image is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter. The order of patterning the four colors is not limited to the above-mentioned order.

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

[4] 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.

[4-1] Liquid Crystal Display Device A method for manufacturing a liquid crystal display device according to the present invention will be described. In the liquid crystal display device according to the present invention, an alignment film is usually formed on the color filter according to the present invention, a spacer is sprayed on the alignment film, and then the liquid crystal cells are formed by bonding with an opposing substrate. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete the process. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by heat firing, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.

A spacer having a size corresponding to a gap (gap) with the facing substrate is used, and a spacer having a size of 2 to 8 μm is usually preferable. A photospacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the facing substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding with the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. .. The degree of decompression in the liquid crystal cell is usually in the range of 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. .. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually in the range of 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

The heat retention at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal display device (panel) is completed by sealing the liquid crystal injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin.
The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a lyotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.

[4-2] Organic EL Display Device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 1, the pixels 20 are formed on the transparent support substrate 10 by the colored resin composition of the present invention. A multicolored organic EL element is produced by laminating an organic illuminant 500 via an organic protective layer 30 and an inorganic oxide film 40 on a blue color filter on which the above is formed.

As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. The organic EL element 100 produced in this manner can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.

<Parthalocyanine compound A>
A phthalocyanine compound A having the following chemical structure synthesized based on Example 30 of JP-A-05-345861 was used.

<Parthalocyanine compound B>
Mix 5.00 g (18.8 mmol) of tetrachlorophthalonitrile, 3.32 g (18.8 mmol) of 2-cyclohexyl-5-methylphenol, 3.89 g (28.2 mmol) of potassium carbonate and 50 mL of acetonitrile and bring to 70 ° C. It was heated and stirred as it was for 4 hours. After completion of the reaction, the mixture was cooled to room temperature, and the reaction solution was filtered and concentrated. By recrystallizing the obtained residue with acetonitrile, 4.70 g of a mixture of Intermediate A and Intermediate B (yield 59%, purity 77.9%, intermediate A / intermediate B = 73/23) was obtained. Obtained. This purity is a value of area% calculated from the result of high performance liquid chromatography analysis.

Intermediate A ¹ H-NMR (CDCl ₃ )
δ: 1.28 (m, 1H), 1.45 (m, 4H), 1.76 (dd, 1H), 1.86 (dd, 2H), 1.96 (dd, 2H), 2.21 (S, 3H), 3.03 (q, 1H), 5.96 (s, 1H), 6.92 (d, 1H), 7.23 (d, 1H)

3.00 g (7.15 mmol) of a mixture of Intermediate A and Intermediate B, 0.69 g (2.14 mmol) of zinc iodide and 7.2 g of benzonitrile were mixed and reacted at 170 ° C. for 6.5 hours. After completion of the reaction, the reaction solution was cooled and charged into 20 mL of methanol. The produced solid content was filtered, washed with methanol and water, and dried under reduced pressure at 50 ° C. to obtain 2.62 g (yield 84%) of phthalocyanine compound B.

When 1 mg of phthalocyanine compound B was dissolved in 100 mL of DMSO (dimethylsulfoxide) and the visible absorption spectrum was measured with an ultraviolet-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a 1 cm square quartz cell, the maximum absorption was obtained. wavelength 651.0Nm, molar extinction coefficient (epsilon) was 4.08 × 10 ^5.

<Dispersant A: Dispersant "BYK-LPN6919" manufactured by Big Chemie>
A methacrylic acid-based AB block copolymer composed of an A block having a prosolvent group and a B block having a nitrogen atom-containing functional group. It has the repeating units of the following formulas (2a) and (3a), and does not have the repeating units of the following formula (1a). The amine value is 120 mgKOH / g and the acid value is 1 mgKOH / g or less.

The content ratios of the following formulas (2a) and (3a) in all the repeating units are 33.3 mol% and 6.7 mol%, respectively.

<Alkali-soluble resin A>
A separable flask with a cooling tube is prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate is charged, and after nitrogen substitution, the temperature of the reaction vessel is raised to 90 ° C. by heating with an oil bath while stirring. did.

On the other hand, 30 parts by mass of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, and t-butylperoxy-2-ethyl in the monomer tank. 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by mass of n-dodecyl mercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged in the chain transfer agent tank, and the temperature of the reaction tank was charged. Was stabilized at 90 ° C., and then dropping was started from the monomer tank and the chain transfer agent tank to start the polymerization. The dropping was carried out over 135 minutes while maintaining the temperature at 90 ° C., and 60 minutes after the dropping was completed, the temperature was raised to 110 ° C.

After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas 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 in the reaction vessel, and the temperature was 110 ° C. Was reacted for 9 hours.
After cooling to room temperature, an alkali-soluble resin A having a polystyrene-equivalent weight average molecular weight Mw of 9000 and an acid value of 101 mgKOH / g measured by GPC was obtained.

<Alkali-soluble resin B>
148.0 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 7.3 parts by mass of styrene, 91.0 parts by mass of glycidyl methacrylate and 61.7 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Continued to do. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.8 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 39.0 parts by mass of succinic anhydride and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw of the alkali-soluble resin B thus obtained measured by GPC was 8000, and the acid value was 88 mgKOH / g.

<Alkali-soluble resin C>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate and 10 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 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 at 120 ° C. for 6 hours. Then, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin C thus obtained was 9000, and the acid value was 25 mgKOH / g.

<Preparation of green pigment dispersion>
C. I. Pigment Green 58 is 13.29 parts by mass, dispersant A is 2.95 parts by mass in terms of solid content, alkali-soluble resin A is 3.81 parts by mass in terms of solid content, and propylene glycol monomethyl ether acetate is 79.95 parts by mass as a solvent. A stainless steel container was filled with 225 parts by mass (including a solvent derived from the dispersant A and a solvent derived from the alkali-soluble resin A) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and dispersed with a paint shaker for 6 hours. After completion of the dispersion, the zirconia beads were separated to prepare a green pigment dispersion.

<Preparation of yellow pigment dispersion>
C. I. Pigment Yellow 138 is 12.06 parts by mass, dispersant A is 3.01 parts by mass in terms of solid content, alkali-soluble resin A is 6.03 parts by mass in terms of solid content, and propylene glycol monomethyl ether acetate is 78.9 parts by mass as a solvent. A stainless steel container is filled with 225 parts by mass (including a solvent derived from dispersant A and a solvent derived from alkali-soluble resin A) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm, and dispersed with a paint shaker for 6 hours to obtain a yellow pigment. A dispersion was prepared.

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

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

<Photopolymerization initiator B>
Oxime ester compounds having the following chemical structure ((4-acetoxyimimino-5-[9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -5-oxopentanoate methyl)) Was used.

<Photopolymerization initiator C>
A compound having the following chemical structure was used.

<Photopolymerization initiator D>
A compound having the following chemical structure was used.

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

<Surfactant A>
Mega Fuck F-559 (manufactured by DIC Corporation)

<Surfactant B>
BYK-330 (manufactured by Big Chemie)

<Preparation of colored resin composition>
Each component shown in Table 1 was mixed at the solid content ratio shown in Table 1 to prepare a colored resin composition. Propylene glycol monomethyl ether acetate (PGMEA) was used so that the total solid content in the colored resin composition was 18% by mass.

<Measurement of brightness>
The colored resin composition was applied on a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC Inc.) with a spin coater, and then dried at 80 ° C. for 2 minutes. Next, the entire surface was exposed with a 2 kW high-pressure mercury lamp at an exposure amount of 30 mW / cm ² and 40 mJ / cm ² . Then, the thermosetting treatment was carried out at a temperature of 230 ° C. for 20 minutes.
Table 2 shows the brightness when the transmission spectrum of the obtained colored substrate was measured by a spectrophotometer U-3310 manufactured by Hitachi, Ltd. and the chromaticity was sy = 0.568 with the SB2 light source.

As is clear from Table 2, when the colored resin composition containing the phthalocyanine compound (1) is used as the green colorant as in Example 1, the brightness is high, while Comparative Examples 2 to 3 In place of the phthalocyanine compound (1), the phthalocyanine compounds B and C. I. When the colored resin composition containing Pigment Green 58 is used, the brightness is low.
The phthalocyanine compound (1) has molecules that easily associate with each other due to the π-π interaction between the phthalocyanine rings and the π-π interaction between the general formulas (2), and in particular, it has a fluorine atom having a small atomic radius. It is considered that the packing between the molecules becomes denser and the brightness becomes higher due to the formation of aggregates between the two molecules.

<Preparation of colored resin composition>
Each component shown in Table 3 was mixed at the solid content ratio shown in Table 3 to prepare a colored resin composition. Propylene glycol monomethyl ether acetate (PGMEA) was used so that the total solid content in the colored resin composition was 18% by mass.

<Measurement of contrast>
The colored resin composition was applied on a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by AGC Inc.) with a spin coater, and then dried at 80 ° C. for 2 minutes. Next, the entire surface was exposed with a 2 kW high-pressure mercury lamp at an exposure amount of 30 mW / cm ² and 40 mJ / cm ² . Then, the thermosetting treatment was carried out at a temperature of 230 ° C. for 20 minutes to obtain a colored substrate having a film thickness of 2 μm.
Table 4 shows the contrasts measured by the contrast meter CT-1B manufactured by Tsubosaka Electric Co., Ltd. using the colored substrate.

As is clear from Table 4, among the colored resin compositions containing the phthalocyanine compound (1), those containing the photopolymerization initiator (d1) having a fluorene skeleton as in Example 2 are as shown in Comparative Examples 3 to 5. The contrast is higher than that containing other photopolymerization initiators.

In the phthalocyanine compound (1), molecules are easily associated with each other due to π-π interaction between phthalocyanine rings and π-π interaction between groups represented by the general formula (2), and fluorine having a small atomic radius. By having an atom, the packing between the molecules becomes denser and the brightness is improved by forming an aggregate between the two molecules, but the association further progresses and an aggregate is easily formed. Therefore, it is considered that the contrast tends to decrease due to light scattering by the agglomerates. Therefore, by including a photopolymerization initiator (d1) having a fluorene skeleton, the π-π interaction between the fluorene skeleton and the phthalocyanine ring promotes the formation of an aggregate between two molecules of the phthalocyanine compound (1). However, it is considered that the formation of aggregates due to excessive association is suppressed, light scattering is less likely to occur, and the decrease in contrast can be suppressed. On the other hand, as in Comparative Examples 6 to 9, instead of the phthalocyanine compound (1) as the green colorant, chlorine-substituted phthalocyanine compounds B and C.I. I. When Pigment Green 58 is used, since the π-π interaction between the phthalocyanine rings is weak in those colorants, aggregates are not formed regardless of the type of photopolymerization initiator, and the contrast does not decrease. it is conceivable that.

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 modifications can be made without departing from the intent and scope of the invention.

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

Claims (5)

A colored resin composition containing (A) a colorant, (B) a solvent, (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
A colored resin composition, wherein the photopolymerization initiator (D) contains a photopolymerization initiator (d1) having a fluorene skeleton.

(In the formula (1), A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a fluorine atom, or a group represented by the following general formula (2). However, one or more of A ^{1 to} A ¹⁶ Represents a fluorine atom, and one or more of A ^{1 to} A ¹⁶ represents a group represented by the following general formula (2).)

(In the formula (2), X represents a divalent linking group. The benzene ring in the formula (2) may have an arbitrary substituent. * Represents a bond.) The colored resin composition according to claim 1, wherein the content ratio of the phthalocyanine compound having the chemical structure represented by the general formula (1) is 5% by mass or more in the total solid content. The colored resin composition according to claim 1 or 2, wherein the photopolymerization initiator (d1) contains a photopolymerization initiator represented by the following general formula (I).

In formula (I), R ^d1 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
R ^d2 represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent.
p represents 0 or 1.
R ^d3 represents any monovalent substituent. q represents an integer from 0 to 3.
R ^d4 and R ^d5 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aromatic ring group which may have a substituent. R ^d4 and R ^d5 may be coupled to each other to form a ring. ) A color filter having pixels created by using the colored resin composition according to any one of claims 1 to 3. An image display device having the color filter according to claim 4.

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