JP2020201373A - Coloring composition for color filters, and photosensitive coloring resin composition - Google Patents

Abstract

To provide a coloring composition for color filters that has excellent storage stability and can form a pattern having excellent surface smoothness.SOLUTION: A coloring composition for color filters contains (A) a colorant and (B) organic solvent. The (A) colorant contains a phthalocyanine compound having a chemical structure represented by a predetermined formula containing a zinc atom. The (B) organic solvent has a sp value of 8.8-9.2(cal/cm3) 1/2. The content of the (A) colorant is 18 mass% or less.SELECTED DRAWING: None

Description

The present invention relates to a coloring composition for a color filter and a photosensitive coloring resin composition.

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 to 3).

Japanese Unexamined Patent Publication No. 2009-051896 International Publication No. 2014/157387 Japanese Unexamined Patent Publication No. 2014-43556

In Patent Documents 1 to 3, a phthalocyanine compound as a dye is mixed with a specific organic solvent and used, but as a result of examination by the present inventor, the solubility in the organic solvent is not sufficient and the storage stability is high. It was found that it was poor and that the flatness of the pattern obtained when the pattern was formed using the mixture was insufficient.
Therefore, an object of the present invention is to provide a coloring composition for a color filter, which has good storage stability and can form a pattern having excellent flatness.

As a result of diligent studies by the present inventor, it has been found that the above problems can be solved by using a specific phthalocyanine compound as a colorant and further using an organic solvent having a sp value in a specific range. I arrived.
That is, the present invention has the following configurations [1] to [7].

[1] A coloring composition for a color filter containing (A) a colorant and (B) an organic solvent.
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
(B) A coloring composition for a color filter, wherein the sp value of the organic solvent is 8.8 to 9.2 (cal / cm ³ ) ^1/2 .

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

[2] The coloring composition for a color filter according to [1], wherein the content ratio of the colorant (A) is 18% by mass or less.
[3] The color filter according to [1] or [2], wherein the organic solvent (B) contains an organic solvent (b1) having an sp value of 9.0 (cal / cm ³ ) ^1/2 or less. Coloring composition.
[4] The coloring composition for a color filter according to any one of [1] to [3], wherein the organic solvent (b1) contains propylene glycol monomethyl ether acetate.

[5] The method according to any one of [1] to [4], wherein the organic solvent (B) contains an organic solvent (b2) having an sp value of 9.3 (cal / cm ³ ) ^1/2 or more. Coloring composition for color filters.

[6] A photosensitive coloring resin composition containing the coloring composition for a color filter according to any one of [1] to [5], (C) an alkali-soluble resin, and (D) a photopolymerization initiator.
[7] The photosensitive colored resin composition according to [6], which further contains (E) a photopolymerizable monomer.

According to the present invention, it is possible to provide a coloring composition for a color filter, which has good storage stability and can form a pattern having excellent flatness.

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 "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.
Further, in the present invention, the "total solid content" means all the components other than the solvent contained in the coloring composition for a color filter or the photosensitive coloring resin composition.

[1] Components of Coloring Composition for Color Filter The components of the coloring composition for color filter of the present invention will be described below. The coloring composition for a color filter according to the present invention may contain (A) a coloring agent, (B) an organic solvent, and if necessary, additives other than the above-mentioned components.

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

In the formula (1), A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, 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 color filter coloring composition of the present invention contains a phthalocyanine compound (1). In the phthalocyanine compound (1), it is considered that the molecules easily associate with each other due to the π-π interaction between the phthalocyanine rings and the π-π interaction between the groups represented by the general formula (2), and the brightness becomes high.
The phthalocyanine compound (1) is sometimes used as a dye, but it has been found by the present inventors that it is difficult to sufficiently dissolve in an organic solvent and that it aggregates and precipitates over time.

If the phthalocyanine compound (1) was not sufficiently dissolved in the organic solvent, the particles of the phthalocyanine compound (1) were agglomerated by heat curing, and the contrast was lowered by light scattering by the generated agglomerates. It is considered that the surface texture of the color filter also tends to deteriorate.

According to the study by the present inventors, the sp value of the (B) organic solvent contained in the coloring composition for a color filter is reduced to 8.8 to 9.2 (cal / cm ³ ) ^1/2 to obtain a phthalocyanine compound ( It was found that 1) was sufficiently dissolved in an organic solvent to improve storage stability, and it was possible to suppress a decrease in contrast and deterioration of surface properties. The phthalocyanine compound (1) has a structure having a rigid and hydrophobic isoindole that tends to have a low sp value, a central zinc metal that tends to have a high sp value, and a group represented by the above formula (2). B) It is considered that the phthalocyanine compound (1) is sufficiently solvated with the organic solvent (B) and becomes stable by setting the sp value of the organic solvent to about 8.8 to 9.2.

(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 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.

Examples of the halogen atom in A ^{1 to} A ¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom. Fluorine is used from the viewpoint of adjusting the hue to the optimum color as the green dye used in the color filter and increasing the brightness. Atoms are preferred.

(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 affinity with 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 affinity with an organic solvent.
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, it tends to suppress entanglement between molecules and suppress aggregation, and when it is at least the above upper limit value, the affinity with an organic solvent is improved and the stability over time is improved. Tends to improve.
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 the methyl group or the ethyl group is used from the viewpoint of the degree of freedom of suppressing entanglement between molecules. Preferably, an ethyl group is more preferred.

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 set to the lower limit value or more, a steric repulsion effect is produced and agglutination in an organic solvent tends to be suppressed, and when it is set to the upper limit value or less, affinity with an organic solvent can be ensured and stability over time. Tends to improve.

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 groups having one free valence, such as a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, and a heptalene 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 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, frazane 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 heat resistance is improved by stacking π-π between the dye molecules, and the decrease in brightness due to the decomposition of the dye is suppressed. From the viewpoint of this, it is preferable that the number of substitutions is 1 for one benzene ring.
Further, 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 stacking having a close-packed structure is possible. From the viewpoint of becoming, the p-position is preferable.

One or more of A ^{1 to} A ¹⁶ represents a group represented by the general formula (2), and one or more of A ^{1 to} A ⁴ is said from the viewpoint of solubility in an organic solvent and brightness. A group represented by the general 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 said. It is preferable that the group is represented by the general formula (2) and one or more of A ^{13 to} A ¹⁶ is a group represented by the general formula (2), and among A ^{1 to} A ⁴ , it is preferable. Two 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 among A ^{9 to} A ¹² It is more preferable that two 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 viewpoint of the color required by the color filter and the affinity with the organic solvent, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ and A ¹⁵ are the general formulas (2). ), And it is particularly preferable that A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ and A ¹⁶ are halogen atoms.

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

As a method for producing the phthalocyanine compound (1), a known method can be adopted. 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. As a modern dye, 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 the 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 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 solvent salt milling is preferably used.

The content ratio of the (A) colorant in the coloring composition for a color filter of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and 8% by mass in the coloring composition for a color filter. The above is further preferable, 10% by mass or more is particularly preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, 40% by mass or less is further preferable, 20% by mass or less is further preferable, and 14% by mass or less. The following is particularly preferable, and 11% by mass or less is most preferable. When it is set to the lower limit value or more, the desired chromaticity and film thickness as a color filter tend to be obtained, and when it is set to the upper limit value or less, the storage stability tends to be improved.

The content ratio of the phthalocyanine compound (1) in the coloring composition for a color filter of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass in the coloring composition for a color filter. The above is further preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, 40% by mass or less is further preferable, 20% by mass or less is further preferable, 14% by mass or less is particularly preferable, and 11% by mass or less. The following are the most preferable. When it is set to the lower limit value or more, the desired chromaticity and film thickness as a color filter tend to be obtained, and when it is set to the upper limit value or less, the storage stability tends to be improved.

When other colorants are contained, the content ratio thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, and further preferably 5% by mass or more in the coloring composition for a color filter. It is preferably 50% by mass or less, more preferably 30% by mass or less, further preferably 10% by mass or less, and particularly preferably 6% by mass or less. When it is set to the lower limit value or more, the desired chromaticity and film thickness as a color filter tend to be obtained, and when it is set to the upper limit value or less, the brightness tends to be improved.

[1-2] (B) Organic Solvent The coloring composition for a color filter of the present invention contains (B) an organic solvent. The organic solvent (B) has a function of dissolving or dispersing (A) a colorant and other components to adjust the viscosity.

In the coloring composition for a color filter of the present invention, the sp value of the organic solvent (B) is 8.8 to 9.2 (cal / cm ³ ) ^1/2 . The sp value (Solubility Parameter, solubility parameter) of an organic solvent is the square root of the cohesive energy density in the regular solution theory, and it is known that the smaller the difference between the two sp values, the better the solubility. This sp value is calculated by the calculation method of Fedors, and the unit is (cal / cm ³ ) ^1/2 (hereinafter, the description of the unit is omitted). As the sp value of one kind of organic solvent alone, for example, a value up to one digit after the decimal point described in International Publication No. 2014/057846 and International Publication No. 2015/087811 can be adopted. In the case of a mixed organic solvent, this sp value means the sp value of all organic solvents, and the sp value of each organic solvent contained therein is weighted averaged by the molar ratio, and is a value up to two digits after the decimal point. To adopt.

(B) The sp value of the organic solvent is not particularly limited as long as it is 8.8 to 9.2, but it is preferably 8.80 or more, more preferably 8.85 or more, further preferably 8.90 or more, and 8.95. The above is particularly preferable, 9.20 or less is preferable, 9.15 or less is more preferable, 9.10 or less is further preferable, and 9.05 or less is particularly preferable. When it is at least the lower limit value, the affinity of the phthalocyanine compound (1) with the organic solvent of the group represented by the formula (2) tends to be improved, and when it is at least the upper limit value, the phthalocyanine compound tends to be improved. The affinity of the isoindole structure of (1) with the organic solvent tends to be improved.

(B) The organic solvent may be composed of one kind of organic solvent alone, or may be composed of a mixture of two or more kinds of organic solvents. From the viewpoint of solubility and storage stability, an organic solvent (b1) having an sp value of 9.0 or less (hereinafter, may be referred to as "organic solvent (b1)") and an organic solvent having an sp value of 9.3 or more. It is preferably a mixture of an organic solvent (b2) (hereinafter, may be referred to as "organic solvent (b2)").

The sp value of the organic solvent (b1) is not particularly limited as long as it is 9.0 or less, but is preferably 8.9 or less, more preferably 8.8 or less, preferably 7.8 or more, and 8.0 or more. More preferably, 8.2 or more is further preferable, 8.4 or more is further preferable, and 8.6 or more is particularly preferable. When it is set to the upper limit value or less, a hydrophobic field is formed in the organic solvent, and the affinity of the phthalocyanine compound (1) with the isoindole structure tends to be improved, and when it is set to the lower limit value or more, it is excessive. Due to the formation of the hydrophobic field, the precipitation of the phthalocyanine compound (1) due to the deterioration of the affinity with the group represented by the above formula (2) tends to be suppressed.

As a specific example of the organic solvent (b1) having an sp value of 9.0 or less,
Dipropylene glycol methyl-n-butyl ether (sp value: 8.0), dipropylene glycol methyl-n-propyl ether (sp value: 8.0), dipropylene glycol dimethyl ether (sp value: 7.9), propylene glycol Ethers such as methyl-n-butyl ether (sp value: 7.8), propylene glycol methyl-n-propyl ether (sp value: 7.8), tetrahydrofuran (sp value: 8.3);
Acetic acids such as methyl acetate (sp value: 8.8), ethyl acetate (sp value: 8.7), n-propyl acetate (sp value: 8.7), isopropyl acetate (sp value: 8.5);
Diethylene glycol ethyl ether acetate (sp value: 9.0), ethylene glycol methyl ether acetate (sp value: 9.0), diethylene glycol monobutyl ether acetate (sp value: 8.9), ethylene glycol monobutyl ether acetate (sp value: 8) .9), methyl acetate (sp value: 8.8), ethyl acetate (sp value: 8.7), propylene glycol monomethyl ether acetate (sp value: 8.7), n-propyl acetate (sp value: 8. 7), ether esters such as dipropylene glycol methyl ether acetate (sp value: 8.7), 3-methoxybutyl acetate (sp value: 8.7), ethyl ethoxypropionate, etc., and phthalocyanine compounds (1) From the viewpoint of solubility in the coloring composition of, ethers, acetates and ether esters are preferable, and ether esters are more preferable.

The boiling point of the organic solvent (b1) at 1013.25 hPa is not particularly limited, but is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, further preferably 130 ° C. or higher, particularly preferably 140 ° C. or higher, and 190 ° C. or lower. Is more preferable, 180 ° C. or lower is more preferable, 170 ° C. or lower is further preferable, and 160 ° C. or lower is particularly preferable. When it is set to the lower limit value or more, the coating film is prevented from being roughened due to rapid drying when the color filter is formed, and the contrast tends to be stable. When the value is set to the upper limit value or less, the coating film is dried when the color filter is formed. Aggregation of the phthalocyanine compound (1) due to unevenness tends to be reduced.

On the other hand, the sp value of the organic solvent (b2) is not particularly limited as long as it is 9.3 or more, but is preferably 9.5 or more, more preferably 9.7 or more, still more preferably 9.9 or more, and 10.1. The above is particularly preferable, 11.8 or less is preferable, 11.3 or less is more preferable, 10.8 or less is further preferable, and 10.3 or less is particularly preferable. By setting the value to the lower limit or higher, a hydrophilic field is formed in the organic solvent, and the affinity of the phthalocyanine compound (1) with the group represented by the formula (2) tends to be improved, and the upper limit is set. By doing the following, the precipitation of the phthalocyanine compound (1) due to the deterioration of the affinity with the indole structure due to the formation of an excessive hydrophilic field tends to be suppressed.

As a specific example of the organic solvent (b2) having an sp value of 9.3 or more,
Alcohols such as n-propanol (sp value: 11.8), 1,2,5,6-tetrahydrobenzyl alcohol (sp value: 11.3);
Diethylene glycol ethyl ether (sp value: 10.9), 3-methoxybutanol (sp value: 10.9), propylene glycol monomethyl ether (sp value: 10.2), propylene glycol-n-propyl ether (sp value: 9) .8), Propylene glycol-n-butyl ether (sp value: 9.7), Dipropylene glycol methyl ether (sp value: 9.7), Dipropylene glycol-n-propyl ether (sp value: 9.5), Ether alcohols such as dipropylene glycol-n-butyl ether (sp value: 9.4), tripropylene glycol methyl ether (sp value: 9.4), tripropylene glycol-n-butyl ether (sp value: 9.3) ;
Cyclic ketones such as cyclopentanone (sp value: 10.0) and cyclohexanone (sp value: 9.9);
1,4-Butandiol diacetate (sp value: 9.6), 1,3-butylene glycol diacetate (sp value: 9.5), 1,6-hexanediol diacetate (SP value: 9.5) , Propylene glycol diacetate (sp value: 9.6), ethyl lactate acetate (sp value: 9.6), triacetin (sp value: 10.2) and other di / triesters;
Examples thereof include lactones such as γ-butyrolactone (SP value: 9.9) and ε-caprolactone (SP value: 9.6), from the viewpoint of solubility of the phthalocyanine compound (1) in the coloring composition. Ether alcohols, cyclic ketones, and diesters are preferable, and ether alcohols are more preferable.

The boiling point of the organic solvent (b1) at 1013.25 hPa is not particularly limited, but is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, particularly preferably 110 ° C. or higher, and 160 ° C. or lower. Is preferable, 150 ° C. or lower is more preferable, 140 ° C. or lower is further preferable, and 130 ° C. or lower is particularly preferable. When it is set to the lower limit value or more, the coating film is prevented from being roughened due to rapid drying when the color filter is formed, and the contrast tends to be stable. When the value is set to the upper limit value or less, the coating film is dried when the color filter is formed. Aggregation of the phthalocyanine compound (1) due to unevenness tends to be reduced.

The content ratio of the organic solvent (B) in the coloring composition for a color filter of the present invention is not particularly limited, but is preferably 40% by mass or more, more preferably 50% by mass or more, and 60% by mass in the coloring composition for a color filter. The above is further preferable, 70% by mass or more is further preferable, 75% by mass or more is particularly preferable, 99% by mass or less is preferable, 97% by mass or less is more preferable, 95% by mass or less is further preferable, and 93% by mass or less. The following is even more preferable, and 91% by mass or less is particularly preferable. When it is at least the lower limit value, the viscosity suitable for coating tends to be maintained, and when it is at most the upper limit value, it tends to be easy to form a coating film uniformly.

When the (B) organic solvent in the coloring composition for a color filter of the present invention contains the organic solvent (b1), the content ratio thereof is not particularly limited, but (B) 40% by mass or more is preferable in the organic solvent. , 50% by mass or more is more preferable, 60% by mass or more is further preferable, 70% by mass or more is further preferable, 75% by mass or more is particularly preferable, 95% by mass or less is preferable, and 90% by mass or less is more preferable. , 85% by mass or less is more preferable, and 82% by mass or less is particularly preferable. When the value is equal to or higher than the lower limit, the viscosity is suppressed so that the coating film surface becomes uniform and the contrast tends to be improved. When the value is equal to or higher than the upper limit, the sp value is prevented from being excessively lowered, and the phthalocyanine compound ( The aggregation of 1) tends to be suppressed.

Further, when the (B) organic solvent in the coloring composition for a color filter of the present invention contains the organic solvent (b2), the content ratio thereof is not particularly limited, but (B) 1% by mass or more is preferable in the organic solvent. 5, 5% by mass or more is more preferable, 10% by mass or more is further preferable, 12% by mass or more is further preferable, 15% by mass or more is particularly preferable, 18% by mass or more is most preferable, and 35% by mass or less is preferable. , 30% by mass or less is more preferable, 25% by mass or less is further preferable, and 22% by mass or less is particularly preferable. By setting the value to the lower limit or higher, the affinity of the phthalocyanine compound (1) with the organic solvent of the group represented by the formula (2) tends to be improved, the contrast tends to be improved, and the value is lower than the upper limit. This tends to prevent the sp value from becoming too high and reduce the aggregation of the phthalocyanine compound (1).

[1-3] Other Ingredients The coloring composition for a color filter of the present invention contains (A) a colorant and (B) an organic solvent, but other solids may be further added if necessary. Examples of such a component include a dispersant and a dispersion aid.

When the coloring composition for a color filter of the present invention contains a pigment as (A) a coloring agent, it is preferable to include 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), and SOLSPERSE (registered trademark, manufactured by Ruburi). 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.

When the coloring composition for a color filter of the present invention contains a pigment, a pigment derivative or the like may be further 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 phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group, etc. are directly on the pigment skeleton or an alkyl group, an aryl group, a complex 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 plurally substituted in one pigment skeleton, 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.

[2] Components of Photosensitive Colored Resin Composition Each component of the photosensitive colored resin composition of the present invention will be described below. The photosensitive coloring resin composition according to the present invention contains the coloring composition for a color filter of the present invention, (C) an alkali-soluble resin, and (D) a photopolymerization initiator as essential components, and if necessary, the above. It may contain additives other than the components.

[2-1] Coloring Composition for Color Filter The photosensitive coloring resin composition of the present invention includes the coloring composition for a color filter of the present invention. That is, the photosensitive coloring resin composition of the present invention contains components derived from the coloring composition for a color filter of the present invention such as (A) a colorant and (B) an organic solvent, but the coloring for a color filter of the present invention It may further contain a colorant or an organic solvent that is not derived from the composition.

The content ratio of the (A) colorant in the photosensitive coloring resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more in the total solid content of the photosensitive coloring resin composition. Preferably, 12% by mass or more is further preferable, 15% by mass or more is particularly preferable, 60% by mass or less is more preferable, 50% by mass or less is more preferable, 40% by mass or less is further preferable, and 30% by mass or less is particularly preferable. .. When it is at least the above lower limit value, it tends to be easy to adjust the content ratio of the organic solvent in the photosensitive coloring resin composition, and when it is at least the above upper limit value, the stability over time of the photosensitive coloring resin composition Tends to improve.

The content ratio of the phthalocyanine compound (1) in the photosensitive coloring resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more in the total solid content of the photosensitive coloring resin composition. Preferably, 8% by mass or more is further preferable, 10% by mass or more is further preferable, 12% by mass or more is particularly preferable, 15% by mass or more is most preferable, 50% by mass or less is preferable, and 40% by mass or less is more preferable. It is preferable that it is 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less. When it is set to the lower limit value or more, the phthalocyanine compound (1) tends to associate efficiently and the brightness and contrast tend to be improved, and when it is set to the upper limit value or less, the aggregation of the phthalocyanine compound (1) is alleviated. , The photosensitive colored resin composition tends to improve the stability over time.

The content ratio of the organic solvent (B) in the photosensitive coloring resin composition of the present invention is not particularly limited, but is preferably 30% by mass or more, more preferably 40% by mass or more, and 50% by mass in the photosensitive coloring resin composition. % Or more is further preferable, 60% by mass or more is further preferable, 70% by mass or more is particularly preferable, 80% by mass or more is most preferable, 99% by mass or less is preferable, 95% by mass or less is more preferable, and 90% by mass or more. % Or less is more preferable, and 85% by mass or less is particularly preferable. When it is at least the lower limit value, the viscosity suitable for coating tends to be maintained, and when it is at most the upper limit value, it tends to be easy to form a coating film uniformly.

When the photosensitive coloring resin composition of the present invention contains an organic solvent (b1), the content ratio thereof is not particularly limited, but 20% by mass or more is preferable, and 40% by mass or more is preferable in the photosensitive coloring resin composition. More preferably, 60% by mass or more is further preferable, 70% by mass or more is further preferable, 75% by mass or more is particularly preferable, 99% by mass or less is preferable, 95% by mass or less is more preferable, and 90% by mass or less is particularly preferable. More preferably, 85% by mass or less is particularly preferable. When the value is at least the lower limit, the viscosity of the photosensitive colored resin composition can be suppressed, the coating film surface becomes uniform, and the contrast tends to be improved. When the value is at least the upper limit, the sp value is It tends to prevent the decrease too much and suppress the aggregation of the phthalocyanine compound (1).

When the photosensitive coloring resin composition of the present invention contains an organic solvent (b2), the content ratio thereof is not particularly limited, but it is preferably 1% by mass or more, preferably 5% by mass or more in the photosensitive coloring resin composition. More preferably, 10% by mass or more is further preferable, 12% by mass or more is further preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is particularly preferable. More preferably, 25% by mass or less is particularly preferable. By setting the value to the lower limit or higher, the affinity of the phthalocyanine compound (1) with the organic solvent of the group represented by the formula (2) tends to be improved, the contrast tends to be improved, and the value is lower than the upper limit. By doing so, the sp value is prevented from becoming too high, and the aggregation of the phthalocyanine compound (1) tends to be reduced.

[2-2] (C) Alkali-soluble resin The photosensitive 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-7-207211A, 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 photosensitive coloring resin composition of the present invention is used for forming a color filter, the heat resistance of the photosensitive coloring resin composition is improved, and the photosensitive coloring resin composition is improved in heat resistance. The strength of the pixels formed by using the colored resin composition 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, etc. 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 photosensitive colored resin composition. It is preferable to contain one or more of these. 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 methyl carbitol, ethyl carbitol, butyl carbitol; Triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; benzene, toluene, xylene, octane, Hydrocarbons such as decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate; dimethylformamide, N-methylpyrrolidone, etc. 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 by adding the 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 5 to 90 mol% of repeating units 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, the heat resistance and strength tend to be sufficient by setting the content ratio of the repeating unit derived from the other radically polymerizable monomer to the above lower limit value or more.
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 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 photosensitive 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 to be 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 commercially available 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 Corporation. There are "Denacol EX-171", "Denacol EX-192" and the like.

The structure of such a resin is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 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 100,000, 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, from the viewpoint of patterning characteristics, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable. 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, it is also preferable to have a partial structure represented by the following general formula (II), for example.

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 fused 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 pyrene. Groups such as a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring can be mentioned.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, 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, thienofuran ring, benzoisooxazole ring, benzoiso Thiazol 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, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable, from the viewpoint of developability.
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 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 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.

(C1) 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 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 photosensitive colored resin composition tends to be improved.

When the acrylic copolymer resin (c1) contains a partial structure represented by the general formula (I), the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin (c1) is improved as the other partial structure contained. From the viewpoint of the 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-pentadiin-5-yl group, 1-hexyne-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, the fluorine atom is preferable from the viewpoint of storage stability of the (c1) 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 compounds (1) and (c1) acrylic copolymer resin tends to be improved, and the alkali solubility tends to be improved. The content ratio of the structure increases, 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) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (IV), the content ratio thereof 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 photosensitive 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 photosensitive 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 photosensitive coloring resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more in the total solid content of the photosensitive coloring resin composition. , More preferably 10% by mass or more, still 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 50% by mass or less, still 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.

[2-3] (D) Photopolymerization Initiator The photosensitive 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 initiation 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.

Examples of the photopolymerization initiator include metallocene compounds containing titanosen compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbiimidazole described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, radical activators such as N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone-based compounds and oxime ester-based initiators described in JP-A-2000-80068.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4) Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;

2-Trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5-[β- (2'-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2-( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5- Imidazole derivatives such as diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone;

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

Ethyl benzoate derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzfenadine;
Anthrone derivatives such as Benz anthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentagenyl-Ti-bis-phenyl, dicyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentagenyl-Ti-bis-2,4,6-trifluoropheni-1-yl, Dicyclopentagenyl-Ti-2,6-dipuroolofeni-1-yl, dicyclopentagenyl-Ti-2,4-difluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,3 , 4,5,6-pentafluoropheni-1-yl, dimethylcyclopentagenyl-Ti-bis-2,6-difluoropheni-1-yl, dicyclopentagenyl-Ti-2,6-difluoro- Titanocene derivatives such as 3- (pill-1-yl) -pheni-1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Etc. α-aminoalkylphenyl compounds;
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) esterone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Oxime ester compounds such as -1- (O-acetyloxime).

Among these, an oxime ester-based compound (oxime ester-based photopolymerization initiator) is preferable from the viewpoint of sensitivity and surface properties.
Oxime ester compounds have a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in their structure, so they are highly sensitive to small amounts and stable to thermal reactions. Therefore, it is possible to design a highly sensitive photosensitive colored resin composition with a small amount. In particular, an oxime ester-based compound having a carbazole ring, which may have a substituent, is preferable from the viewpoint of light absorption of the exposure light source for i-ray (365 nm).

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

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

The number of carbon atoms of the alkyl group in R ^21a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity to exposure, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less, more preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a cyclopentylethyl group, a propyl group and the like.
Substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl. Examples thereof include a group or an N-acetyl-N-acetoxyamino group, which is preferably unsubstituted from the viewpoint of ease of synthesis.

Examples of the aromatic ring group in R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive colored resin composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, further preferably 12 or less, and particularly preferably 8 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a frill group, a fluorenyl group and the like. Among these, a phenyl group, a naphthyl group or a fluorenyl group is preferable from the viewpoint of developability, and phenyl. A group or a fluorenyl group is more preferable.
The substituents that the aromatic ring group may have include a hydroxyl group, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a carboxy group, a halogen atom, and an amino group. , Amid group, alkyl group and the like. From the viewpoint of developability, a hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable. Further, examples of the substituent in the alkyl group which may have a substituent and the alkoxy group which may have a substituent include a hydroxyl group, an alkoxy group, a halogen atom and a nitro group.
Among these, from the viewpoint of developability, R ^21a is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and further preferably a methyl group. ..

Further, R ^21b is an arbitrary substituent containing an aromatic ring or a heteroaromatic ring, but has a carbazolyl group or a substituent which may have a substituent from the viewpoint of solubility in a solvent and sensitivity to exposure. Preferred examples thereof include a thioxanthonyl group which may be used, a diphenylsulfide group which may have a substituent or a fluorenyl group which may have a substituent, and a group in which these groups and a carbonyl group are linked. Among these, from the viewpoint of light absorption of the exposure light source for i-ray (365 nm), a carbazolyl group which may have a substituent or a carbazolyl group which may have a substituent and a carbonyl group are linked. Groups are preferred.

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less, more preferably 5 or less. Specific examples of the alkanoyl group include an acetyl group, an ethyloyl group, a propanoyl group, a butanoyl group and the like.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group and the like, and from the viewpoint of easiness of synthesis, the substituent should be unsubstituted. Is preferable.

The carbon number of the allylloyl group in R ^22a is not particularly limited, but from the viewpoint of solubility in a solvent and sensitivity, it is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, more preferably. It is 10 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group and the like, and from the viewpoint of easiness of synthesis, it is preferably unsubstituted. ..

Among the compounds represented by the general formula (I-1), they are represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorption of the exposure light source for i-line (365 nm). Examples include compounds.

In the above formula (I-2) or (I-3), R ^21a and R ^22a are synonymous with the above general formula (I-1).
R ^23a represents an alkyl group which may have a substituent.
R ^24a represents an alkyl group which may have a substituent, an allylloyl group which may have a substituent, a heteroallyloyl group which may have a substituent, or a nitro group.
The benzene ring constituting the carbazole ring may be further condensed by an aromatic ring to form a polycyclic aromatic ring.

The number of carbon atoms of the alkyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and the like.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of easiness of synthesis, there is no substitution. Is preferable.
Among these, R ^23a is more preferably an ethyl group from the viewpoint of solubility in a solvent and easiness of synthesis.

The number of carbon atoms of the alkyl group in R ^24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, and further. It is preferably 5 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group and the like.
Examples of the substituent that the alkyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of easiness of synthesis, there is no substitution. Is preferable.

The carbon number of the allylloyl group in R ^24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. It is preferably 10 or less, more preferably 9 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of easiness of synthesis, an ethyl group is used. Is preferable.

The number of carbon atoms of the heteroallyloyl group in R ^24a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , More preferably 10 or less, still more preferably 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthyl group, a chloronaphthyl group, a bromonaphthyl group and the like.
Examples of the substituent that the heteroarylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and there is no substituent from the viewpoint of easiness of synthesis. It is preferably a substitution.
Among these, as R ^24a , an aryloyl group which may have a substituent is preferable, and a benzoyl group is more preferable, from the viewpoint of sensitivity.

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

Commercially available products of such oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd., or N- manufactured by ADEKA Corporation. 1919, NCI-930, NCI-831 and the like.

Specific examples of the oxime ester-based compound include, but are not limited to, the compounds exemplified below.

One of these 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 photosensitive coloring resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but it is preferably 1% by mass or more, preferably 2% by mass or more, in the total solid content of the photosensitive coloring resin composition. Is more preferable, 3% by mass or more is further preferable, 4% by mass or more is particularly preferable, 15% by mass or less is preferable, 10% by mass or less is more preferable, 8% by mass or less is further preferable, and 6% by mass or less is Especially 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.

[2-4] Other Solids The photosensitive 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 and a surfactant.

[2-4-1] 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, (Referred to as "ethyleney compound") is preferable. The ethylenic compound is a compound having an ethylenic double bond such that when the photosensitive coloring 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 at least the above lower limit value, the development and dissolution characteristics tend to be good, and when it is at least the above upper limit value, 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 sensitivity of the coating film and shortening of the developing time, it is preferable to use the polymerizable monomer described in JP2013-195974A.

When the photosensitive colored resin composition of the present invention contains a photopolymerizable monomer, the content ratio of the photopolymerizable monomer is not particularly limited, but it is usually 0% by mass or more in the total solid content of the photosensitive colored resin composition. It is preferably 5% by mass 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 more. It is mass% or less, more preferably 40 mass% or less, and particularly preferably 30 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.

[2-4-2] Surfactant As the surfactant, 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, and more preferably 0.05% by mass or more in the total solid content of the photosensitive coloring resin composition. , More preferably 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, further preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less. ..

[3] Preparation of Coloring Composition for Color Filter The method for preparing the coloring composition for a color filter of the present invention is not particularly limited, but (A) a colorant, (B) an organic solvent, and if necessary, other additives and the like. Can be mixed and prepared.
(B) When a mixture of the organic solvent (b1) and the organic solvent (b2) is used as the organic solvent, for example, after mixing the organic solvent (b1) and the organic solvent (b2) in an arbitrary container, there. It can be obtained by adding (A) a colorant, another additive, or the like, stirring the mixture for several minutes to several hours, and dissolving each component in an organic solvent.

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

When the colorant does not contain a pigment, a color filter color composition, an alkali-soluble resin, a photopolymerization initiator, and in some cases, 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.

When preparing a colorant containing a pigment, it is preferable to first weigh each predetermined amount of the pigment, solvent and dispersant, and in the dispersion treatment step, disperse the pigment containing the pigment 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 pigment is made into fine particles by performing this dispersion treatment, the coating characteristics of the photosensitive coloring 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.

When producing a photosensitive coloring resin composition, a photosensitive coloring resin composition containing a pigment can be obtained by mixing the color filter coloring composition with a pigment dispersion liquid.

[5] 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 photosensitive coloring resin composition.

[5-1] 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 thin film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

[5-2] 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 pixel images of usually red, green, and blue. The photosensitive colored resin composition is preferably used as a coating liquid for forming green pixels (resist pattern) (hereinafter, may be abbreviated as "green resist") among the red, green, and blue pixels. .. 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 photosensitive 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 photosensitive 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 coloring resin composition for a black matrix is used, a photosensitive coloring 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 photosensitive 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.

[5-3] Formation of Pixels A photosensitive coloring 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. Through this photomask, a pixel image is formed by image exposure, development, and if necessary, thermosetting or photocuring. A color filter image can be formed by performing this operation on each of the three color photosensitive colored resin compositions of red, green, and blue.

The photosensitive 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.

[5-4] Drying of Coating Film The coating film after coating the photosensitive colored resin composition on the substrate is preferably dried 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.

[5-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on a coating film of a photosensitive 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 thereof 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.

[5-6] Development Step In the color filter according to the present invention, a coating film using the photosensitive coloring 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 used. An image can be formed on a substrate and produced by developing with an aqueous solution containing and. 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.

[5-7] 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.

[5-8] 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.

[6] 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.

[6-1] 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 cell is 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 hardened 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 liotropic 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.

[6-2] 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 photosensitive colored resin composition of the present invention is used on the transparent support substrate 10. A multicolored organic EL element is produced by laminating an organic illuminant 500 on a blue color filter on which pixels 20 are formed via an organic protective layer 30 and an inorganic oxide film 40.

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.

<Binder resin A>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing 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 of the binder resin A thus obtained measured by GPC was about 9000, the acid value was 25 mgKOH / g, and the double bond equivalent was 260 g / mol.

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

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

<Surfactant A>
Mega Fuck F-554 (manufactured by DIC Corporation)

<Preparation of coloring compositions 1 to 7 for color filters>
10.0 parts by mass of phthalocyanine compound A, 72.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA, sp value: 8.7 (cal / cm ³ ) ^1/2 ) as an organic solvent, propylene glycol monomethyl ether (PGME) , Sp value: 10.2 (cal / cm ³ ) ^1/2 ) was filled in 18.0 parts by mass in a glass tube and stirred with a stirrer for 3 hours to prepare a coloring composition 1 for a color filter.
Coloring compositions 2 to 7 for color filters were prepared in the same manner except that the ratios of each component were set to the ratios shown in Table 1.

<Evaluation of sediment>
Each of the prepared coloring compositions was put into a 50 ml screw tube and allowed to stand at 23 ° C. for 1 week. After that, when the glass tube was slowly turned upside down, the presence or absence of sediment at the bottom of the screw tube was confirmed. In the case where sediment was generated, it was confirmed that the sediment of the phthalocyanine compound was aggregated and adhered to the bottom of the screw pipe. The results are shown in Table 3.

<Preparation of Photosensitive Colored Resin Compositions 1 to 7>
Next, each component was mixed so that the solid content ratio and the solvent ratio were as shown in Table 2, and photosensitive colored resin compositions 1 to 7 having a total solid content content ratio of 18% by mass were prepared. "Solid content ratio" means the ratio (mass%) of the solid content of various components to the total solid content. Further, the "solvent ratio" means the ratio (mass%) of the amount of various solvents to the total solvent, and the amount of various solvents includes the amount derived from the coloring composition for a color filter.

<Surface roughness evaluation>
Each photosensitive colored resin composition was applied to a 50 mm square glass substrate (AN100 manufactured by AGC Inc.) having a thickness of 0.7 mm using a spin coater, and dried on a hot plate at 90 ° C. for 90 seconds. The obtained coating film, by 2kW high-pressure mercury lamp, and exposed ^{23mW / cm 2, 40mJ / cm} 2 and so as. The ultraviolet irradiation at this time was performed under air. The substrate was cured by heating in an oven at 230 ° C. for 30 minutes to obtain a resist film having a film thickness of 2.5 μm. The surface roughness Sa (μm) of the resist film thus obtained was measured under the following conditions using a scanning white interference microscope VS1530 manufactured by Hitachi High-Technologies Corporation. The results are shown in Table 3.

(Measurement condition)
-Light source: 520 White (520 nm)
-Objective lens: 10x-Measurement device: Piezo-Measurement mode: Phase
-Field of view size: 640 x 480 Pipels (466.42 μm x 350.48 μm)

<Measurement of contrast and brightness>
Each photosensitive 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 on a hot plate at 80 ° C. for 3 minutes. The obtained coating film was exposed to 23 mW / cm ² and 100 mJ / cm ² with a 2 kW high-pressure mercury lamp. The ultraviolet irradiation at this time was performed under air. The substrate was cured by heating in an oven at 230 ° C. for 30 minutes to obtain a resist film.
The transmission spectrum of the resist film was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the brightness when the chromaticity was sy = 0.400 with a C light source and the contrast meter CT-1B manufactured by Tsubosaka Electric Co., Ltd. The results of the contrast measured in Table 3 are shown in Table 3.

The "sp value of the organic solvent" in Table 3 means the sp value of all organic solvents contained in the coloring composition for a color filter, and is a value calculated by weighted averaging the sp values of each organic solvent by their molar ratios. Is.

From Table 3, the coloring compositions for color filters of Examples 1 to 5 have no sediment and have good storage stability, and the surface roughness of the coated substrate prepared by using the photosensitive coloring resin composition containing the same. The brightness and contrast were also good. On the other hand, in the coloring compositions for color filters of Comparative Examples 1 and 2, there was a precipitate, the surface roughness of the coated substrate was large, and the contrast was insufficient.

The sp value (Solubility Parameter, solubility parameter) of an organic solvent is the square root of the cohesive energy density in the regular solution theory, and it is known that the smaller the difference between the two sp values, the better the solubility.

Propylene glycol monomethyl ether acetate is a typical example of an organic solvent generally used in coloring compositions for color filters and photosensitive coloring resin compositions, and its sp value is 8.7. When the sp value of the organic solvent is less than 8.8 as in Comparative Example 1, the phthalocyanine compound (1) having low compatibility with propylene glycol monomethyl ether acetate becomes an aggregate, and the phthalocyanine compound (1) becomes aggregated. The undissolved phthalocyanine compound (1) settled in the coloring composition because it could not be sufficiently dissolved in the organic solvent, and protrusions were formed on the coated substrate prepared using the photosensitive coloring resin composition containing the compound. Foreign matter was generated, the surface roughness was large, and the contrast was insufficient.

Further, when the sp value of the organic solvent exceeds 9.2 as in Comparative Example 2, the phthalocyanine compound (1) having a hydrophobic skeleton becomes an aggregate, and the phthalocyanine compound (1) is contained in the organic solvent. The undissolved phthalocyanine compound (1) settles in the coloring composition because it cannot be sufficiently dissolved in the coating substrate, and becomes a protruding foreign substance in the coated substrate prepared using the photosensitive coloring resin composition containing the compound. The surface roughness was large and the contrast was insufficient.

On the other hand, as in Examples 1 to 5, the coloring composition for a color filter of the present invention has a hydrophobic skeleton in which the sp value of the organic solvent is 8.8 to 9.2 and tends to have a low sp value. The phthalocyanine compound (1) having a central zinc metal that tends to have a high sp value and a group represented by the above formula (2) is effectively solvated, and the phthalocyanine compound (1) is placed in an organic solvent. The surface roughness of the coated substrate prepared by using the photosensitive coloring resin composition containing the phthalocyanine compound (1) which can be sufficiently dissolved and is not dissolved in the coloring composition for a color filter without sedimentation. Is small, and it is considered that the contrast has improved.

As described above, the coloring composition for a color filter of the present invention has good storage stability, the aggregation of the coloring agent is suppressed even on the coated substrate, the flatness of the pattern surface is improved, and the image display device is manufactured. It is considered that the elution of the resist component into the liquid crystal layer or the like can be suppressed.

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 (7)

A coloring composition for a color filter containing (A) a colorant and (B) an organic solvent.
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
(B) A coloring composition for a color filter, wherein the sp value of the organic solvent is 8.8 to 9.2 (cal / cm ³ ) ^1/2 .

(In the formula (1), A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, 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 formula (2) may have an arbitrary substituent. * Represents a bond.) The coloring composition for a color filter according to claim 1, wherein the content ratio of the colorant (A) is 18% by mass or less. The coloring composition for a color filter according to claim 1 or 2, wherein the organic solvent (B) contains an organic solvent (b1) having an sp value of 9.0 (cal / cm ³ ) ^1/2 or less. The coloring composition for a color filter according to any one of claims 1 to 3, wherein the organic solvent (b1) contains propylene glycol monomethyl ether acetate. The color filter according to any one of claims 1 to 4, wherein the organic solvent (B) contains an organic solvent (b2) having an sp value of 9.3 (cal / cm ³ ) ^1/2 or more. Coloring composition. A photosensitive coloring resin composition containing the coloring composition for a color filter according to any one of claims 1 to 5, (C) an alkali-soluble resin, and (D) a photopolymerization initiator. The photosensitive colored resin composition according to claim 6, further containing (E) a photopolymerizable monomer.

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