JP2019113732A - Coloring resin composition, color filter, and image display device - Google Patents

Abstract

To provide a coloring resin composition that makes it possible to obtain a color filter with practically sufficient brightness.SOLUTION: A coloring resin composition has (A) a colorant, (B) a solvent, (C) a binder resin, and (D) a photopolymerization initiator. The (A) colorant has a phthalocyanine compound having zinc. In a repeating unit of the (C) binder resin, a carboxyl group is sufficiently separated from the main chain to ensure high flexibility.SELECTED DRAWING: None

Description

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

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

  In recent years, higher luminance, higher contrast, and higher color gamut have been required for color filters. As a coloring material for determining the color of a color filter, a pigment is generally used from the viewpoint of heat resistance, light resistance, etc. However, the pigment can not meet the market requirements particularly for high luminance, and the color It is actively studied to use a dye instead of a pigment as a material. For the green pixel, studies have been conducted using a specific phthalocyanine compound as a dye (see, for example, Patent Documents 1 and 2).

JP, 2009-051896, A WO 2004/157387

As a result of investigations by the present inventor, it was found that, with the colored resin compositions described in Patent Document 1 and Patent Document 2, the luminance of the obtained color filter is not sufficient for practical use.
Then, an object of this invention is to provide the coloring resin composition which can obtain a color filter with sufficient brightness practically.

As a result of intensive investigations conducted by the present inventor, the inventors have found that the above problems can be solved by using a specific phthalocyanine compound as a colorant and further using a specific binder resin as a binder resin, leading to the present invention. The
That is, the present invention has the following configurations [1] to [4].

[1] A colored resin composition comprising (A) a colorant, (B) a solvent, (C) a binder resin, and (D) a photopolymerization initiator,
The (A) coloring agent includes a phthalocyanine compound having a chemical structure represented by the following general formula (1),
Colored resin composition characterized by said (C) binder resin containing binder resin (c-1) which has a repeating unit represented by following General formula (I).

(In formula (1), each of A ^{1 to} A ¹⁶ independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that one or more of A ^{1 to} A ¹⁶ are used. Represents a group represented by the following general formula (2))

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

(In formula (I), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a trivalent hydrocarbon group which may have a substituent.
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a divalent hydrocarbon group which may have a substituent. )

[2] The colored resin composition according to [1], wherein the (A) colorant further contains a pigment.
[3] A color filter having pixels produced using the colored resin composition according to [1] or [2].
The image display apparatus which has a color filter as described in [4] [3].

  According to the present invention, it is possible to provide a colored resin composition capable of obtaining a color filter having sufficient luminance for practical use.

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

The constituent features and the like of the present invention will be described in detail below, but these are merely examples of embodiments of the present invention, and the present invention is not limited to these contents.
In addition, "(meth) acrylic", "(meth) acrylate" etc. shall mean "acrylic and / or methacryl", "acrylate and / or methacrylate" etc., for example, "(meth) acrylic acid" By acrylic acid and / or methacrylic acid is meant. Moreover, "total solid content" shall mean all components other than the solvent component mentioned later contained in a pigment dispersion liquid or a coloring resin composition.

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

[1] Constituent Components of Colored Resin Composition Each constituent component of the colored resin composition of the present invention will be described below. The colored resin composition according to the present invention comprises (A) a colorant, (B) a solvent, (C) a binder resin, and (D) a photopolymerization initiator as essential components, and if necessary, other than the above components. And the like may be blended.
Each component will be described below.

[1-1] (A) Colorant The (A) colorant contained in the colored resin composition of the present invention is a phthalocyanine compound having a chemical structure represented by the following general formula (1) (hereinafter referred to as “phthalocyanine compound ( May be referred to as “1)”.

In Formula (1), each of A ^{1 to} A ¹⁶ independently represents 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 represent a group represented by the following general formula (2).

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

  When the coloring agent (A) contained in the colored resin composition of the present invention contains the phthalocyanine compound (1), the luminance of the obtained color filter becomes high. Although the detailed mechanism has not been clarified, the phthalocyanine compound (1) becomes soluble in a solvent by having a group represented by the above general formula (2) in the phthalocyanine skeleton, and at the time of baking, the general formula (2) It is considered that heat resistance is dramatically improved by pigmentation and decomposition being suppressed by the π-π interaction between the two) and the π-π interaction between the phthalocyanine skeletons, and the brightness is increased even after baking.

(A ^{1 to} A ¹⁶ )
In the formula (1), each of A ^{1 to} A ¹⁶ independently represents 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 represent a group represented by the following general formula (2).

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

Examples of the halogen atom in A ^{1 to} A ¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom, but a fluorine atom is preferable from the viewpoint of adjusting to an optimum hue as a green pigment used for a color filter.

(X)
X in the general formula (2) represents a divalent linking group. Although it does not specifically limit as a bivalent coupling group, An oxygen atom, a sulfur atom, or -N (R ^<a1> )-group is mentioned. R ^a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among them, an oxygen atom or a sulfur atom is preferable from the viewpoint of the stability of the phthalocyanine compound (1) at the time of baking and the formation of a hydrogen bond with the binder resin (c-1) in forming a colored resin composition. Atoms are more preferred.

(A substituent which a benzene ring may have)
In addition, the benzene ring in Formula (2) may have any 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), aryl group, aryloxy group (-OR ^B group (wherein R ^B represents an aryl group)), aryloxycarbonyl group (-COOR ^B group (where R ^B is aryl) represents a group.)), with alkyl groups contained in these groups (-R ^a group) and an aryl group (-R ^B group), it may be further substituted by these substituents. Among these, an alkoxycarbonyl group is preferable from the viewpoint of the solubility in a solvent and the formation of a hydrogen bond with the binder resin (c-1) when forming a colored resin composition.

Although the alkyl group contained in these groups may be linear, branched, or cyclic, it may be soluble in a solvent or used as a binder resin (c-1) in the colored resin composition. From the viewpoint of suppressing inhibition of hydrogen bond formation, a linear form is preferable.
The carbon number of the alkyl group is not particularly limited, but is usually 1 or more and 2 or more, 6 or less is preferable, 5 or less is more preferable, and 4 or less is more preferable. The solubility to the solvent of a phthalocyanine compound (1) tends to improve by setting it as more than the said lower limit, and the hydrogen bond with binder resin (c-1) is formed by setting it as the said upper limit or less. It tends to be
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group, and from the viewpoint of suppressing the inhibition of hydrogen bond formation with the binder resin (c-1) A methyl group or an ethyl group is preferable, and an ethyl group is more preferable.

The aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The carbon number of the aryl group is not particularly limited, but generally 4 or more and 6 or more is preferable, 12 or less is preferable, 10 or less is more preferable, and 8 or less is more preferable. The solubility to the solvent of a phthalocyanine compound (1) tends to improve by setting it as more than the said lower limit, and the hydrogen bond with binder resin (c-1) is formed by setting it as the said upper limit or less. It tends to be

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. As an aromatic hydrocarbon ring group, groups, such as a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, which have one free valence, are mentioned, for example.
The aromatic heterocyclic ring in the aromatic heterocyclic group may be a single ring or a fused ring. The aromatic heterocyclic group is, for example, a furan ring, a thiophene ring, a pyrrole ring, a 2H-pyran ring, a 4H-thiopyran ring, a pyridine ring, a 1,3-oxazole ring, an isoxazole having one free valence. Ring, 1,3-thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazan ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,3,5-triazine ring, benzofuran ring, 2-benzofuran ring, benzothiophene Ring, 2-benzothiophene ring, 1H-pyrrolidine ring, indole ring, isoindole ring, indolizine ring, 2H-1-benzopyran ring, 1H-2-benzopyran ring, quinoline ring, isoquinoline ring, 4H-quinolidine ring, benzo Imidazole ring, 1H-indazole ring, quinoxaline ring, quinazoline ring, cinnoline And groups such as ring, phthalazine ring, 1,8-naphthyridine ring, purine ring, pteridine ring and the like.

One or more of A ^{1 to} A ¹⁶ represent a group represented by the general formula (2), but from the viewpoint of solubility in a solvent, one or more of A ^{1 to} A ⁴ have the general formula 2), one or more of A ^{5 to} A ⁸ being a group represented by the general formula (2), and one or more of A ^{9 to} A ¹² being a group represented by the general formula It is preferable that it is a group represented by 2), and at least one of A ^{13 to} A ¹⁶ is a group represented by the general formula (2), and two or more of A ^{1 to} A ⁴ Is a group represented by the general formula (2), and two or more of A ^{5 to} A ⁸ are a group represented by the general formula (2), two or more of A ^{9 to} A ¹² There is a group represented by the general formula (2), and is more preferably a group in which at least two of a ¹³ to a ¹⁶ is represented by the general formula (2).
In particular, from the viewpoint of color tone required for color filters and solubility in solvents, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ and A ¹⁵ have the above general formula (2) It is particularly preferable that A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ and A ¹⁶ be a halogen atom.

  Examples of the phthalocyanine compound (1) include the following.

  A well-known method can be employ | adopted as a manufacturing method of phthalocyanine compound (1), for example, the method of Unexamined-Japanese-Patent No. 05-345861 can be employ | adopted.

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

  As yellow pigments, 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, 63, 65, 73, 74, 75, 81, 83, 86, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 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, 69, 170, 172, 173, 175, 176, 180, 181, 182, 183, 184, 188, 189, 190, 191, 191, 191, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, and a 1: 1 complex of azobarbituric acid with nickel represented by the following formula (i) or a compatible isomer thereof And the like (hereinafter, may be referred to as “a nickel azo complex represented by the formula (i)”) and the like.

  Moreover, as said other compound, the compound etc. which are represented by following formula (ii) are mentioned.

  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 a nickel azo complex represented by the formula (i) are preferable, and C.I. I. Pigment Yellow 83, 138, 139, 180, 185, and a nickel azo complex represented by Formula (i) are more preferable.

Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. The specific compound as described in Unexamined-Japanese-Patent No. 2010-168531 is mentioned as the specific example.
Among those classified as dyes by color index, C.I. I. As solvent dyes, C.I. I. 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 acid dyes, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 or derivatives thereof It 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, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141 and the like. Furthermore, C.I. I. As a mordant dye C.I. I. Mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, etc., 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, 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 dye decomposition suppression at the time of heat baking, C.I. I. It is preferable that it is at least 1 sort (s) chosen from the group which consists 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, more preferably 0.04 μm or less. At the time of atomization of the pigment, a technique such as solvent salt milling described above is suitably used.

  The content of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, based on the total solid content of the colored resin composition. % Or more is more preferable, 15% by mass or more is particularly preferable, 45% by mass or less is preferable, 40% by mass or less is more preferable, 35% by mass or less is more preferable, 30% by mass or less is more preferable, 25% by mass or less Is particularly preferred. By setting it to the above lower limit value or the like, color characteristics such as luminance tend to be improved, and by setting it to the above upper limit value, pattern formation deterioration at the time of color filter production tends to be suppressed.

  Although the content rate is not specifically limited when it includes other coloring agents, 1 mass% or more is preferable with respect to the total solid of a colored resin composition, 5 mass% or more is more preferable, 8 mass% or more is more preferable. 10 mass% or more is further more preferable, 15 mass% or more is particularly preferable, 40 mass% or less is preferable, 35 mass% or less is more preferable, 30 mass% or less is more preferable, 25 mass% or less is particularly preferable. By setting the content to the above lower limit or more, thermal decomposition at the time of thermal firing at the time of color filter formation tends to be suppressed, and by setting the above upper limit or less, pattern formation deterioration at the time of color filter formation tends to be suppressed There is.

[1-2] (B) Solvent (B) The solvent has the function of dissolving or dispersing the coloring agent, the binder resin, the photopolymerization initiator, and other components in the colored resin composition of the present invention to adjust the viscosity. Have.
As the solvent (B), any solvent can be used as long as it can dissolve or disperse each component.

  As such solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl -3-Methoxybutanol Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;

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

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

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethyl pentanone;
Acetonitrile, nitriles such as benzonitrile, and the like can be mentioned.

  Commercially available solvents corresponding to the above include Mineral Spirit, Valsol # 2, Apco # 18 Solvent, Apcosynner, Socar Solvent No. 1 and No. 1 2. Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl carosolve, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all are trade names) and the like. One of these solvents may be used alone, or two or more thereof may be used in combination.

When forming the pixels of the color filter by photolithography, a solvent having a boiling point of 100 to 200 ° C. (pressure of 1013.25 [hPa] conditions, hereinafter the same applies to all the boiling points) is selected. Is preferred. More preferably, it has a boiling point of 120 to 170 ° C.
Among the above solvents, glycol alkyl ether acetates are preferable in terms of good balance of coating properties, surface tension and the like and relatively high solubility of components in the composition.

  Moreover, although glycol alkyl ether acetates may be used independently, you may use another solvent together. Particularly preferable solvents used in combination are glycol monoalkyl ethers. Among them, propylene glycol monomethyl ether is particularly preferable in view of the solubility of the component in the composition. In addition, since the glycol monoalkyl ethers have high polarity, and the addition amount is too large, the pigment tends to aggregate, and the storage stability tends to decrease, for example, the viscosity of the colored resin composition obtained later increases. 5 mass%-30 mass% are preferable, and, as for the ratio of glycol monoalkyl ether in a solvent, 5 mass%-20 mass% are more preferable.

It is also preferable to use a solvent having a boiling point of 150 ° C. or more in combination. By using such a solvent having a high boiling point in combination, although the colored resin composition becomes difficult to dry, it has an effect of making it difficult to cause the mutual destruction of the pigment dispersion by rapid drying. The content of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass with respect to the solvent (B). By setting the lower limit value or more, for example, there is a tendency that it is easy to avoid that a coloring material component or the like precipitates and solidifies at the tip of the slit nozzle and causes foreign matter defects. It tends to be easy to prevent the drying rate from becoming slow and causing problems such as poor tact in the vacuum drying process and pin marks of prebaking.
The solvent having a boiling point of 150 ° C. or more may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, a solvent having a boiling point of 150 ° C. or more may not be separately contained.
As preferred high boiling point solvents, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate Acetate, triacetin and the like can be mentioned.

When forming a pixel of a color filter by an inkjet method, a solvent having a boiling point of usually 130 ° C. or more and 300 ° C. or less, preferably 150 ° C. or more and 280 ° C. or less is suitable. By setting the content to the above lower limit or more, the uniformity of the obtained coating film tends to be good, and by setting the above upper limit or less, the residual solvent at the time of firing tends to be easily reduced.
In addition, the vapor pressure of the solvent may be usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the obtained coating film.

  In the color filter production by the ink jet method, since the ink emitted from the nozzles is extremely fine, such as several to several tens pL, the solvent evaporates and the ink is concentrated before it lands around the nozzle opening or in the pixel bank.・ There is a tendency to dry up. In order to avoid this, it is preferable that the boiling point of the solvent be high, and specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or more, particularly preferably 220 ° C. or more. The high boiling point solvent having a boiling point of 180 ° C. or more is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more in the entire solvent contained in the colored resin composition. By setting the content to the lower limit value or more, the effect of preventing evaporation of the solvent from droplets tends to be sufficiently exhibited.

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

  On the other hand, when the solvent contains an alcohol, the discharge stability in the ink jet method may be deteriorated. Therefore, it is preferable to make alcohol 20 mass% or less in a total solvent, 10 mass% or less is more preferable, and 5 mass% or less is especially preferable.

  The content of the solvent in the colored resin composition of the present invention is not particularly limited, but is usually 99% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less. By setting the content to the upper limit value or less, there is a tendency that the coating film is easily formed. On the other hand, the lower limit of the solvent content is usually 70% by mass or more, preferably 75% by mass or more, more preferably 78% by mass or more, in consideration of the viscosity and the like suitable for coating.

[1-3] (C) Binder Resin The colored resin composition of the present invention contains (C) a binder resin. By containing the binder resin (C), the film curability by photopolymerization and the solubility by the developer can be compatible.
The binder resin (C) in the colored resin composition of the present invention is a binder resin (c-1) having a repeating unit represented by the following general formula (I) (hereinafter referred to as "binder resin (c-1)" There is a case.

In formula (I), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a trivalent hydrocarbon group which may have a substituent.
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a divalent hydrocarbon group which may have a substituent.

  The colored resin composition of the present invention contains the binder resin (c-1), but the carboxy group in the repeating unit represented by the above general formula (I) is sufficiently separated from the main chain and the flexibility is high. (4) It is easy to arrange so as to be exposed to the outside of the resin molecule without forming a strong hydrogen bond between carboxy groups. By forming a bond such as a hydrogen bond between the central metal site and the ether bond site in the phthalocyanine compound (1) and the carboxy group in the binder resin (c-1), the resin covers the phthalocyanine compound (1), It is considered that the decomposition reaction of the phthalocyanine compound (1) at the time of the heat curing treatment is inhibited, resulting in high brightness.

(R ² )
In formula (I), R ² represents a trivalent hydrocarbon group which may have a substituent. As a trivalent hydrocarbon, a trivalent aliphatic hydrocarbon group is mentioned, for example.
Examples of the trivalent aliphatic hydrocarbon group include linear ones, branched ones, cyclic ones and combinations thereof.
The carbon number of the trivalent aliphatic hydrocarbon group is not particularly limited, but is preferably 1 or more and 2 or more, more preferably 3 or more, and usually 15 or less and 10 or less, and 8 or less is more preferably 5 The following are more preferable. By setting the content within the above range, a hydrogen bond is easily formed with the phthalocyanine compound (1), and the luminance tends to be improved.
The following are mentioned as a specific example of a trivalent aliphatic hydrocarbon group.

  Examples of the substituent which the trivalent hydrocarbon group may have include an alkoxy group, an aryloxy group, an aryloxythio group, a halogen atom and the like.

(R ⁴ )
In formula (I), R ⁴ represents a divalent hydrocarbon group which may have a substituent. As a bivalent hydrocarbon, a bivalent aliphatic hydrocarbon group and a bivalent aromatic hydrocarbon ring group are mentioned, for example.
Examples of the divalent aliphatic hydrocarbon group include linear, branched, cyclic and combinations thereof.
The carbon number of the divalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more and 2 or more, 3 or more is more preferable, 4 or more is particularly preferable, and 15 or less and 10 or less is preferable The following are more preferable, and 6 or less are more preferable. By setting the content to the above lower limit or more, the hydrogen bond between the phthalocyanine compound (1) and the carboxy group of the binder resin (c-1) tends to be formed hard, and the content less than the above upper limit causes the phthalocyanine compound to be formed. The formation of hydrogen bonds between (1) and the carboxy group of the binder resin (c-1) tends to be maintained.
Specific examples of the divalent aliphatic hydrocarbon group include ethylene group, propylene group, ethenylene group, cyclohex-4-ene-1,2-diyl group, cyclohexa-1,2-diyl group and the like. Among these, from the viewpoint of promoting the formation of a hydrogen bond with the carboxy group of the binder resin (c-1), an ethylene group, an ethenylene group, and a cyclohex-4-ene-1,2-diyl group are preferable.

  On the other hand, the carbon number of the divalent aromatic hydrocarbon ring group is not particularly limited, but generally 6 or more is preferable and 12 or less is preferable. By setting the content to the above lower limit value or more, the π-π interaction with the phthalocyanine compound (1) tends to be promoted, and by setting the content to the above upper limit value or less, the color filter preparation process of the binder resin (c-1) There is a tendency that the decrease in luminance due to yellowing at the time of firing can be suppressed.

  The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring and a triphenylene ring, having two free valences. And groups such as acenaphthene ring, fluoranthene ring and fluorene ring.

  Examples of the substituent which the divalent hydrocarbon group may have include an alkoxy group, a halogen atom, and a carboxy group.

Although binder resin (c-1) has a repeating unit represented by the said General formula (I), it may further contain another repeating unit.
Another repeating unit is represented by the following general formula (II) from the viewpoint of forming a hydrogen bond with the phthalocyanine compound (1) and improving the curability at the time of preparation of the color filter by the ethylenic double bond. Repeating units are preferred.

In formula (II), R ⁵ represents a hydrogen atom or a methyl group.
R ⁶ represents a trivalent hydrocarbon group which may have a substituent.
R ⁷ represents a hydrogen atom or a methyl group.

As the trivalent hydrocarbon group which may have a substituent in R ⁶ , those exemplified for R ² can be preferably applied.

  Moreover, as another repeating unit, the repeating unit represented by the following general formula (III) is preferable from a viewpoint of yellowing suppression at the time of the thermal baking in a color filter preparation process.

In formula (III), R ⁸ represents a hydrogen atom or a methyl group.
R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.

(R ⁹ )
In formula (III), R ⁹ represents a hydrogen atom or a monovalent hydrocarbon group which may have a substituent.
As monovalent hydrocarbon group, a monovalent | monohydric aliphatic hydrocarbon group and a monovalent | monohydric aromatic hydrocarbon ring group are mentioned.

The monovalent aliphatic hydrocarbon group may be linear, branched, cyclic or a combination thereof.
The carbon number of the monovalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, more preferably 5 or more, particularly preferably 7 or more, and usually 20 or less and 18 or less Is preferable, 15 or less is more preferable, and 12 or less is more preferable. By setting the content to the above lower limit or more, yellowing at the time of thermal firing in the color filter manufacturing process tends to be suppressed, and by setting the above upper limit or less, the alkali developability at the color filter manufacturing tends to be improved. .
Specific examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a tetrahydrodicyclopentadienyl group, and a cyclohexyl group. Among these, from the viewpoint of suppressing yellowing due to heat, a methyl group or tetrahydrodicyclopentadienyl group is preferable.

  The number of carbon atoms in the monovalent aromatic hydrocarbon group is not particularly limited, but is preferably 6 or more and 12 or less. By setting the content to the above lower limit or more, the π-π interaction with the phthalocyanine compound (1) tends to be promoted, and by setting the above upper limit or less, the luminance is reduced due to yellowing at the time of firing of the color filter manufacturing process. Tend to be suppressed.

  The aromatic hydrocarbon ring in the monovalent aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring and a triphenylene ring, having one free valence. And groups such as acenaphthene ring, fluoranthene ring and fluorene ring.

  Examples of the substituent which the monovalent hydrocarbon group may have include an alkoxy group, an aryloxy group, a halogen atom and the like.

  Further, as another repeating unit, a repeating unit represented by the following general formula (IV) is preferable from the viewpoint of promoting the π-π interaction with the phthalocyanine compound (1).

In formula (IV), R ¹⁰ represents a hydrogen atom or a methyl group.

  Although the content rate of the repeating unit represented by the said General formula (I) contained in binder resin (c-1) is not specifically limited, 15 mol% or more is preferable, 20 mol% or more is more preferable, 25 mol% or more is further more preferable 30 mol% or more is more preferable, 35 mol% or more is particularly preferable, 80 mol% or less is preferable, 70 mol% or less is more preferable, 60 mol% or less is more preferable, 50 mol% or less is still more preferable, 45 mol% or less Is particularly preferred. The alkali developability is improved by setting the content to at least the lower limit, and the hydrogen bond with the phthalocyanine compound (1) tends to be firmly formed, and the thermal decomposition of the resin itself is obtained by setting the content to the upper limit or less. It tends to be suppressed.

  When the binder resin (c-1) contains a repeating unit represented by the above general formula (II), the content is not particularly limited, but 5 mol% or more is preferable, 10 mol% or more is more preferable, and 12 mol% or more More preferably, 15 mol% or more is more preferable, 18 mol% or more is particularly preferable, 45 mol% or less is preferable, 40 mol% or less is more preferable, 35 mol% or less is more preferable, and 30 mol% or less is particularly preferable. By setting the content to the above lower limit value or more, the content ratio of the ethylenic double bond is increased, and the binder resin (c-1) is polymerized in the vicinity of the phthalocyanine compound (1) to decompose the phthalocyanine compound (1) at the time of thermal firing. In addition, by setting the upper limit value or less, excessive curing at the time of exposure tends to suppress deterioration of the shape at the time of pixel formation at the time of patterning.

  When the binder resin (c-1) contains a repeating unit represented by the above general formula (III), the content is not particularly limited, but 1 mol% or more is preferable, 5 mol% or more is more preferable, and 10 mol% or more More preferably, 15 mol% or more is more preferable, 20 mol% or more is particularly preferable, 25 mol% or more is most preferable, and 50 mol% or less is preferable, 45 mol% or less is more preferable, 40 mol% or less is more preferable, 35 mol% or less Is particularly preferred. By setting the content to the above lower limit or more, yellowing due to thermal decomposition of the resin at the time of producing the color filter tends to be suppressed, and by setting the above upper limit or less, deterioration of the alkali developability tends to be suppressed. .

  When binder resin (c-1) contains the repeating unit represented by the said General formula (IV), the content rate is not specifically limited, 2 mol% or more is preferable, 3 mol% or more is more preferable, 4 mol% or more is More preferably, 5 mol% or more is particularly preferable, 25 mol% or less is preferable, 20 mol% or less is more preferable, 15 mol% or less is more preferable, and 12 mol% or less is particularly preferable. By setting the content to the above lower limit value or more, the π-π interaction with the phthalocyanine compound (1) is promoted, and the thermal decomposition of the phthalocyanine compound (1) tends to be suppressed. Yellowing due to thermal decomposition of the resin itself tends to be suppressed.

  Although the manufacturing method of binder resin (c-1) is not specifically limited, For example, the epoxy which this copolymer has with respect to the copolymer of an epoxy group containing (meth) acrylate and another radically polymerizable monomer It is obtained by adding an unsaturated monobasic acid to at least a part of the group and adding a polybasic acid anhydride to at least a part of the hydroxyl group generated by the addition reaction. In detail, the manufacturing method described in Unexamined-Japanese-Patent No. 2009-053652 is employable.

Although (C) binder resin in the colored resin composition of this invention contains binder resin (c-1), it may further contain other binder resin (c-2).
The other binder resin (c-2) may be used without particular limitation as long as it exhibits a function as a binder resin, but it is described in WO 2016/158668 [1- 6-2] Linear alkali-soluble resin having a carboxy group in the main chain, [1-6-3] Resin in which an epoxy group-containing unsaturated compound is added to the carboxy group portion of the carboxy group-containing resin, [6-2] 1-6-4] (meth) acrylic resin, epoxy (meth) acrylate resin having a [1-6-5] carboxy group, and those described in JP 2012-018374 A and JP 2012-044365 A And resins having side chains containing cyclic ether groups.

  Although the content rate of binder resin (C) is not specifically limited in the colored resin composition of this invention, 5 mass% or more is preferable with respect to the total solid of a colored resin composition, 8 mass% or more is more preferable, and 10 % By mass or more is more preferable, 12% by mass or more is more preferable, 15% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, 30% by mass or less is more preferable, % By mass or less is more preferable, and 20% by mass or less is particularly preferable. When the content is in the above range, the alkali developability and the patterning after firing tend to be good.

  Although the content rate of binder resin (c-1) is not specifically limited in the colored resin composition of this invention, 1 mass% or more is preferable with respect to the total solid of a colored resin composition, and 2 mass% or more is more preferable Preferably, 3% by mass or more is more preferable, 4% by mass or more is more preferable, 5% by mass or more is particularly preferable, and 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less 20 mass% or less is further more preferable, and 10 mass% or less is especially preferable. By making the phthalocyanine compound (1) and the binder resin (c-1) form hydrogen bonds by setting the content to the above lower limit or more, the thermal decomposition inhibiting ability at the time of baking tends to be high, However, the content ratio of the other polymerization components tends to be relatively high, and deterioration of the patterning shape during development tends to be suppressed.

  Moreover, although the content rate of binder resin (c-1) in (C) binder resin of the colored resin composition of this invention is not specifically limited, 5 mass% or more is preferable, 10 mass% or more is more preferable, and 15 mass% The above is more preferable, 20 mass% or more is more preferable, 25 mass% or more is particularly preferable, 30 mass% or more is most preferable, 80 mass% or less is preferable, 60 mass% or less is more preferable, 50 mass% The following is more preferable, and 40% by mass or less is particularly preferable. By setting the content within the above range, the hydrogen bond amount between the phthalocyanine compound (1) and the binder resin (c-1) tends to be appropriate, and the thermal decomposition inhibiting ability at the time of baking tends to be high.

[1-4] (D) Photopolymerization Initiator The colored resin composition of the present invention contains (D) a photopolymerization initiator. By containing the photopolymerization initiator (D), film curability by photopolymerization can be obtained.
The photopolymerization initiator (D) can also be used as a mixture (photopolymerization initiation system) with an accelerator (chain transfer agent) and an additive such as a sensitizing dye which is optionally added. 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 a titanocene compound 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, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone compounds and oxime ester 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 and 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-oxaxide 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-diphenylimidasol dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (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-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, 1-chloroanthraquinone and the like;

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and the like;
2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,1,1 Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, etc .;

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine and the like;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Dicyclopentadienyl-Ti-dichloride, dicyclopentajenyl-Ti-bis-phenyl, dicyclopentajenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Dicyclopentajenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentajenyl-Ti-bis-2,4,6-trifluorophen-1-yl, Dicyclopentajenyl-Ti-2,6-dipulophorenic-1-yl, dicyclopentajenyl-Ti-2,4-difluoropheny-1-yl, dimethylcyclopentajenyl-Ti-bis-2,3 4,4,5-Pentafluorophen-1-yl, dimethylcyclopentajenyl-Ti-bis-2,6-difluorophen-1-yl, dicyclopentadiene Le -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as 1-yl;

2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl -2-Dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 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 Α-aminoalkylphenone compounds such as
1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3- Oxime ester compounds such as [yl] -1- (O-acetyloxime).

Among these, in terms of sensitivity and surface properties, oxime ester compounds are preferable.
The oxime ester compound has both a structure that absorbs ultraviolet light, a structure that transmits light energy, and a structure that generates radicals in its structure, so it is sensitive in a small amount and stable against thermal reaction. It is possible to design a photosensitive resin composition with high sensitivity and small amount. In particular, an oxime ester compound having a carbazole ring which may have a substituent is preferable from the viewpoint of light absorbability to the i ray (365 nm) of the exposure light source.

  As an oxime ester compound, the compound represented by the following general formula (I-1) is mentioned, for example.

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

The carbon number of the alkyl group in R ^21a is not particularly limited, but it is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solubility in solvents and sensitivity to exposure. It is 10 or less, more preferably 5 or less. A methyl group, an ethyl group, a propyl group, a cyclopentyl ethyl group, a propyl group etc. are mentioned as a specific example of an alkyl group.
As a substituent which the alkyl group may have, an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amido group, 4- (2-methoxy-1-methyl) ethoxy-2-methylphenyl A group or N-acetyl-N-acetoxyamino group etc. are mentioned, It is preferable from a viewpoint of synthetic | combination ease that it is non-substituted.

The aromatic ring group in R ^21a includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, still more 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 furyl group, and a fluorenyl group. Among these, a phenyl group, a naphthyl group or a fluorenyl group is preferable from the viewpoint of developability, and phenyl More preferred is a group or a fluorenyl group.
Examples of the substituent which the aromatic ring group may have include a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a carboxy group, a halogen atom and an amino group. And an amido group, an alkyl group and the like, and from the viewpoint of developability, a hydroxyl group and a carboxy group are preferable, and a carboxy group is more preferable. Moreover, a hydroxyl group, an alkoxy group, a halogen atom, a nitro group is mentioned as a substituent in the alkyl group which may have a substituent, and the alkoxy group which may have a substituent.
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 still more preferably a methyl group. .

Also, R ^{21 b} is an optional substituent containing an aromatic ring or hetero aromatic ring, but from the viewpoint of solubility in a solvent and sensitivity to light exposure, R ^{21 b} has a carbazolyl group which may have a substituent, and a substituent Preferable examples include a thioxanthonyl group which may be substituted, a diphenyl sulfide group which may have a substituent, a fluorenyl group which may have a substituent, and a group in which these groups and a carbonyl group are linked. Among these, a carbazolyl group which may have a substituent or a carbazolyl group which may have a substituent and a carbonyl group may be linked from the viewpoint of light absorbability to the i ray (365 nm) of the exposure light source Groups are preferred.

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility in a solvent and sensitivity. 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 and a butanoyl group.
Examples of the substituent which 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 synthesis easiness, it is unsubstituted Is preferred.

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

  Among the compounds represented by the above general formula (I-1), it is represented by the following general formula (I-2) or (I-3) from the viewpoint of light absorbability to i ray (365 nm) of the exposure light source. Compounds are mentioned.

In said formula (I-2) or (I-3), ^R21a and ^R22a are synonymous with said 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 aryloyl group which may have a substituent, a heteroarylyl 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 carbon number of the alkyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably 10 or less, further Preferably it is 5 or less. A methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group etc. are mentioned as a specific example of an alkyl group.
Examples of the substituent which 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 synthesis ease, unsubstituted Is preferred.

The carbon number of the aryloyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less Preferably it is 10 or less, More preferably, it is 9 or less. Specific examples of the aryloyl group include benzoyl and naphthoyl.
Examples of the substituent which the aryloyl 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 synthesis ease, an ethyl group Is preferred.

The carbon number of the heteroaroyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less More preferably, it is 10 or less, More preferably, it is 9 or less. Specific examples of the heteroaryl group include fluorobenzoyl group, chlorobenzoyl group, bromobenzoyl group, fluoronaphthoyl group, chloronaphthoyl group, bromonaphthoyl group and the like.
Examples of the substituent which may be possessed by the heteroaroyl group 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 Substitution is preferred.
Among them, R ^23a is preferably an alkyl group, more preferably an ethyl group, from the viewpoint of solubility in a solvent and easiness of synthesis.

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

  As commercially available products of such oxime ester compounds, OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304 manufactured by Changzhou High-Power Electronics, TR-PBG-314, and N-1919 manufactured by ADEKA NCI-930, NCI-831 and the like.

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

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

In addition to the photopolymerization initiator (D), a chain transfer agent may be further used. The chain transfer agent is a compound having a function of receiving generated radicals and delivering the radicals to other compounds.
As the chain transfer agent, various compounds can be used as long as they have the above-mentioned function. For example, mercapto group-containing compounds, carbon tetrachloride and the like can be mentioned, and the chain transfer effect tends to be high. It is more preferable to use a compound having a mercapto group. This is considered to be because bond cleavage is likely to occur due to the small S—H bond energy, and it is likely to cause a hydrogen abstraction reaction or a chain transfer reaction. It is effective for sensitivity improvement and surface curability.

  As a mercapto group-containing compound, 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, β- Mercapto-group-containing compounds having an aromatic ring such as mercaptonaphthalene and 1,4-dimethyl mercaptobenzene; hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol bis thioglycolate, ethylene glycol Bis (3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxye Lutristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutylate) Rate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxy) Ethyl, 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like, and mercapto group-containing compounds of aliphatic type such as trione etc., and in particular from the viewpoint of surface smoothness, mercapto group The compound which has two or more is preferable.

  Among them, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among mercapto group-containing compounds having an aromatic ring, and trimethylolpropane tris (3- (3) is preferable among aliphatic mercapto group-containing compounds. Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutylate) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trion Masui.

From the viewpoint of sensitivity, aliphatic mercapto group-containing compounds are preferable, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol Tris (3-mercapto propionate), trimethylolpropane tris (3-mercapto butyrate), pentaerythritol tetrakis (3-mercapto butyrate), pentaerythritol tris (3-mercapto butyrate), 1,3,3,5- Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is preferred, and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis. (3 Mercaptobutylate) is more preferable.
These can be used singly or in combination of two or more.

  In the colored resin composition of the present invention, the content ratio of the photopolymerization initiator (D) is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more based on the total solid content of the colored resin composition. 4 mass% or more is more preferable, 6 mass% or more is particularly preferable, 15 mass% or less is preferable, 12 mass% or less is more preferable, 10 mass% or less is more preferable, 9 mass% or less is particularly preferable. By setting the amount to the above lower limit or more, patterning characteristics after development tend to be secured, and by setting the above upper limit or less, the decrease in transmittance due to excessive addition of the photopolymerization initiator tends to be suppressed.

  When the colored resin composition of the present invention contains a chain transfer agent, the content thereof is not particularly limited, but preferably 0.01% by mass or more, and more preferably 0.1% by mass or more based on the total solid content of the colored resin composition Is more preferable, 0.2 mass or more is more preferable, 0.3 mass% or more is particularly preferable, 5 mass% or less is preferable, 2 mass% or less is more preferable, 1 mass% or less is more preferable, 0. 6 mass% or less is especially preferable. Within this range, storage stability and the ability to form a pattern during alkali development tend to be secured.

[1-5] Other Solid Content In the colored resin composition of the present invention, solid components other than the above-described components can be blended, if necessary. Examples of such components include photopolymerizable monomers, dispersants, dispersion aids, surfactants and the like.

[1-5-1] Photopolymerizable Monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “Ethylenic compounds” are preferred. An ethylenic compound is a compound which has an ethylenic double bond which will be addition-polymerized and hardened | cured by the effect | action of a photoinitiator, when the colored resin composition of this invention receives irradiation of an active ray. The monomer in the present invention means a concept opposite to a so-called polymer substance, and also means a concept including dimers, trimers and oligomers in addition to monomers in a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds 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 It is 8 or less, more preferably 7 or less. By setting the content to the above lower limit or higher, the sensitivity tends to be high, and by setting the above upper limit or below, the solubility in a solvent tends to be improved.

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

  Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, methacrylic acid ester in which acrylic acid part of these acrylates is replaced with methacrylic acid part, itaconic acid ester in which itaconic acid part is replaced, crotonic acid ester in which crotonic acid part is replaced or maleic acid is replaced with maleic acid part Ester etc. are mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like.
The ester obtained by the esterification reaction of unsaturated carboxylic acid and polyvalent carboxylic acid and polyvalent hydroxy compound may not necessarily be a single substance, but may be a mixture. Representative examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol And glycerin condensates and the like.

  Examples of the ethylenic compound having a urethane skeleton in which a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound are reacted include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate, isophorone diisocyanate, etc. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane and the like Reaction products thereof.

In addition, as the ethylenic compound used in the present invention, for example, acrylamides such as ethylene bis acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.
In addition, 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 unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a nonaromatic carboxylic acid anhydride to obtain an acid group. Preferred polyfunctional monomers are those having an aliphatic polyhydroxy compound such as pentaerythritol and / or dipentaerythritol in the ester.

One of these monomers may be used alone, or two or more of these monomers may be mixed and used because it is difficult to use a single compound in production. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
As a preferable acid value of the polyfunctional monomer which has an acidic radical, it is 0.1-40 mgKOH / g, Especially preferably, it is 5-30 mgKOH / g. By setting the content to the above lower limit or more, the developing dissolution characteristic tends to be good. By setting the above upper limit or less, the production and handling become good and the photopolymerization performance, the surface smoothness of the pixel, etc. There is a tendency that the curability tends to be good. Therefore, in the case of using two or more kinds of polyfunctional monomers having different acid groups in combination, or in the case of using a polyfunctional monomer having no acid group, the acid group as the entire polyfunctional monomer is adjusted to fall within the above range. Is preferred.

  In the present invention, polyfunctional monomers having a more preferable acid group are mainly succinic acid esters of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture of ingredients. Other polyfunctional monomers of this polyfunctional monomer can also be used in combination. Moreover, the thing as described in stage-of Unexamined-Japanese-Patent No. 2013-140346 can also be used.

  In the 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 JP-A-2013-195971. From the viewpoint of achieving both the sensitivity of the coating film and the shortening of the development time, it is preferable to use the polymerizable monomer described in JP-A-2013-195974.

  The content ratio of these photopolymerizable monomers is usually 0% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass in the total solid content of the colored resin composition of the present invention % Or more, more preferably 20% by mass or more, particularly preferably 25% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less Particularly preferably, it is at most 30% by mass. Further, the ratio to 100 parts by mass of the (A) colorant is usually 0 parts by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 40 parts by mass The amount is more preferably 60 parts by mass or more, usually 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 80 parts by mass or less.

[1-5-2] Dispersing Agent, Dispersing Aid When the colored resin composition of the present invention contains a pigment as the (A) coloring agent, a dispersing agent can be contained for the purpose of stably dispersing the pigment. Among them, use of a polymer dispersant is preferable because the dispersion stability with time is excellent.
As the polymer dispersant, for example, a urethane based dispersant, a polyethyleneimine based dispersant, a polyoxyethylene alkyl ether based dispersant, a polyoxyethylene glycol diester based dispersant, a sorbitan aliphatic ester based dispersant, an aliphatic modified polyester A system dispersant can be mentioned. Specific examples of these dispersants are trade names EFKA (registered trademark, manufactured by BASF Corporation), DisperBYK (registered trademark, manufactured by BIC Chemie Co., Ltd.), Disperon (registered trademark, manufactured by Kushimoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, Laubri) Examples include those manufactured by Zole, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical), JP-A-2013-119568, and the like.

Among the polymer dispersants, in terms of dispersibility and storage stability, block copolymers having a functional group containing a nitrogen atom are preferable, and acrylic block copolymers are more preferable.
As a block copolymer having a functional group containing a nitrogen atom, an A block having a quaternary ammonium base and / or an amino group in a side chain and a B block having no quaternary ammonium base and / or an amino group are included. The A-B block copolymer and / or the B-A-B block copolymer are preferred.

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

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

  The carbon number of the alkyl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less Preferably, it is 4 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Among them, methyl group, ethyl group, propyl group and butyl group are mentioned. It is preferably a group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

  The carbon number of the aryl group which may have a substituent in the above formula (1) is not particularly limited, but is usually 6 or more, preferably 16 or less, and more preferably 12 or less Preferably, it is 8 or less. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group and the like, and among these, phenyl group, methylphenyl group, ethylphenyl group It is preferably a dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group or an ethylphenyl group.

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

Among these, in terms of dispersibility, storage stability, electrical reliability, and developability, R ¹ and R ² are preferably each independently an alkyl group which may have a substituent, and a methyl group or It is more preferable that it is an ethyl group.

  Examples of the substituent which may be possessed by the alkyl group, the aralkyl group or the aryl group in the above formula (1) include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group and the like, and from the viewpoint of easiness of synthesis Substitution is preferred.

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

  These cyclic structures may further have a substituent.

In the above formula (1), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ¹³ -group, and -COOR ¹⁴ -group [ However, R ¹³ and R ^{14 each} represent a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, and the like, and the like, and preferably —COO—R ¹⁴ -Is a group.

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

  The block copolymer preferably has a repeating unit represented by the following formula (2) from the viewpoint of enhancing the compatibility of the dispersing agent with a binder component such as a solvent and the like to improve the dispersion stability.

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

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

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

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

  The block copolymer preferably has a repeating unit represented by the following formula (3) from the viewpoint of enhancing the compatibility of the dispersant with a binder component such as a solvent and the like to improve the dispersion stability.

In the above formula (3), R ⁸ is an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. R ⁹ is a hydrogen atom or a methyl group.

The number of carbon atoms of the alkyl group which may have a substituent in R ⁸ of the above formula (3) is not particularly limited, but it is usually 1 or more, preferably 1 or more, and 10 or less Is preferable, and 6 or less is more preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Among them, methyl group, ethyl group, propyl group and butyl group are mentioned. It is preferably a group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ⁸ of the above formula (3) is not particularly limited, but it is usually 6 or more, preferably 16 or less, and 12 or less Is more preferred. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group and the like, and among these, phenyl group, methylphenyl group, ethylphenyl group It is preferably a dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group or an ethylphenyl group.

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

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
As a substituent which the alkyl group in R ⁸ may have, a halogen atom, an alkoxy group and the like can be mentioned. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain | strand-shaped alkyl group, a halogen atom, an alkoxy group etc. are mentioned. In addition, the linear alkyl group represented by R ⁸ includes both linear and branched.

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

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

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

  Moreover, repeating units other than the repeating unit represented by said General formula (1) may be contained in A block, As an example of such a repeating unit, the above-mentioned (meth) acrylic acid ester type | system | group is mentioned The repeating unit derived from a monomer etc. are mentioned. The content of the repeating unit other than the repeating unit represented by the general formula (1) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the A block.

Repeating units other than the repeating unit represented by the said General formula (2) and the repeating unit represented by the said General formula (3) may be contained in B block, As an example of such a repeating unit , Styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamides such as (meth) acrylamide and N-methylolacrylamide Monomer; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloyl morpholine, and other repeating units derived from such monomers. The content of the repeating unit represented by the general formula (2) and the repeating unit other than the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably Although it is 0-20 mol%, it is most preferable that such a repeating unit is not contained in B block.

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

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

  The molecular weight of the block copolymer is preferably in the range of 1000 to 30,000 in terms of polystyrene equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). When it is within the above range, the dispersion stability becomes good, and there is a tendency that dry foreign matter is less likely to occur at the time of coating by the slit nozzle method.

  Although the said block copolymer can be manufactured by a well-known method, it can be manufactured by living-polymerizing the monomer which introduce | transduces said each repeating unit, for example. As the living polymerization method, those disclosed in JP-A-9-62002, JP-A-2002-31713, P.I. Lutz, P .; Masson et al, Polym. Bull. 12, 79 (1984), B.I. C. Anderson, G. et al. D. Andrews et al, Macromolecules, 14, 1601 (1981), K., et al. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatata, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Articles, 46, 189 (1989), M. Kuroki, T. Aida, J.A. Am. Chem. Soc, 109, 4737 (1987), Tadazo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D., et al. Y. Sogoh, W. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.

  When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the pigment. Is 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, preferably 70 parts by mass or less, more preferably 50 parts by mass or less More preferably, it is 40 parts by mass or less, particularly preferably 30 parts by mass or less. By setting the content in the above range, a coloring resin composition having excellent dispersion stability and high luminance tends to be obtained.

  When the colored resin composition of the present invention contains a pigment, a pigment derivative or the like may be contained as a dispersion aid to improve the dispersibility of the pigment and the dispersion stability. As a pigment derivative, azo type, phthalocyanine type, quinacridone type, benzimidazolone type, quinophthalone type, isoindolinone type, isoindoline type, dioxazine type, anthraquinone type, indanthrene type, perylene type, perinone type, diketopyrrolo Derivatives such as pyrrole pigments and dioxazine pigments can be mentioned. As a substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amido group etc. directly on the pigment skeleton or an alkyl group, an aryl group or a complex What is bonded via a ring group etc. is mentioned, Preferably a sulfonamide group and its quaternary salt, and a sulfonic acid group are mentioned, More preferably, it is a sulfonic acid group. Further, these substituents may be substituted in one pigment skeleton or may be a mixture of compounds having different numbers of substitution. Specific examples of the pigment derivative include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments.

[1-5-3] Surfactant As the surfactant, various types such as anionic, cationic, nonionic and amphoteric surfactants can be used, but there is a possibility of adversely affecting various properties. It is preferable to use a nonionic surfactant in view of the low The content ratio of the surfactant is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0% with respect to the total solid content of the colored resin composition. .1% by mass or more, usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, most preferably 0.3% by mass or less.

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

  In the case of preparing a pigment containing a pigment as a coloring agent, first, a predetermined amount of each of the pigment, the solvent and the dispersant is weighed, and in the dispersion treatment step, the pigment containing the pigment is dispersed to prepare a pigment dispersion. In the dispersion treatment step, a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer and the like can be used. By performing the dispersion process, the coloring material is micronized, so that the coating characteristics of the colored resin composition are improved, and the transmittance of pixels in the product color filter substrate is improved.

When the pigment is dispersed, as described above, it is preferable to appropriately use a dispersing aid, a dispersing resin, and the like.
When dispersion treatment is performed using a sand grinder, it is preferable to use glass beads of 0.1 to several mm in diameter or zirconia beads. The temperature at the time of the dispersion treatment is usually set in the range of 0 ° C. or more, preferably room temperature or more, and usually 100 ° C. or less, preferably 80 ° C. or less. The dispersion time needs to be appropriately adjusted because the appropriate time differs depending on the composition of the pigment dispersion, the size of the apparatus of the sand grinder, and the like.

  A solvent, a binder resin, a photopolymerization initiator, and in some cases components other than the above are mixed with the pigment dispersion obtained by the above dispersion treatment to obtain a uniform dispersion. In the dispersion treatment step and each step of mixing, fine dust may be mixed, so it is preferable to filter the obtained pigment dispersion with a filter or the like.

  When a pigment is not contained as a coloring agent, a coloring agent, a solvent, a binder resin, a photopolymerization initiator, and in some cases components other than the above may be mixed to obtain a uniform solution. It is preferable to filter the obtained solution with a filter or the like.

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

[3-1] Transparent substrate (support)
The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. As the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, thermoplastic resin sheet of polysulfone, epoxy resin, unsaturated polyester resin, poly (meth) acrylic Thermosetting resin sheets, such as system resin, or various glass etc. are mentioned. Among these, glass or a heat resistant resin is preferable from the viewpoint of heat resistance.

  In order to improve surface properties such as adhesiveness, the transparent substrate and the black matrix-forming substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agent, urethane resin etc. You may The thickness of the transparent substrate is usually in the range of 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When thin film formation processing of various resins is performed, the film thickness thereof 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.

[3-2] Black Matrix The color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of usually red, green and blue. The colored resin composition is preferably used as a coating solution for forming a green pixel (resist pattern) among red, green and blue pixels (hereinafter sometimes abbreviated as "green resist"). Coating, heat drying, image exposure, on the resin black matrix formation surface formed on a transparent substrate using the green resist, or on the metal black matrix formation surface formed using a chromium compound or other light shielding metal material Each process of development and heat curing is performed to form a pixel image.

The black matrix is formed on a transparent substrate using a light shielding metal thin film or a colored resin composition for black matrix. As the light shielding metal material, metal chromium, a chromium compound such as chromium oxide or chromium nitride, nickel and a tungsten alloy may be used, and these may be laminated in a plurality of layers.
These metal light-shielding films are generally formed by sputtering, and after forming a desired pattern in the form of a film by a positive photoresist, with regard to chromium, ceric ammonium nitrate and perchloric acid and / or nitric acid The other materials are etched using the etching solution according to the material, and finally a black matrix is formed by 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 a transparent substrate by vapor deposition or sputtering. Next, a coating film of a colored resin composition is formed on the thin film, and then the coating film is exposed and developed using a photomask having a repeating pattern of stripes, mosaics, triangles, etc., to form a resist image. Thereafter, the coating film can be etched to form a black matrix.

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

[3-3] Formation of Pixel Although the method of forming the pixel differs depending on the type of the colored resin composition to be used, here, the case of using a photopolymerizable composition as the colored resin composition will be described as an example.
A colored resin composition of one of red, green and blue is applied on a transparent substrate provided with a black matrix and dried, and then a photomask is overlaid on the coating film, and image exposure is performed via the photomask. A pixel image is formed by development, if necessary, heat curing or light curing. A color filter image can be formed by performing this operation on the colored resin compositions of three colors of red, green and blue.

  The application of the colored resin composition for a color filter can be performed 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 solution used is greatly reduced, and there is no influence of the mist etc. adhering when using the spin coating method, and the generation of foreign matter is further suppressed, etc. From the viewpoint of

  When the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell formation step may become difficult, whereas when it is too small, it becomes difficult to increase the pigment concentration, which is desirable. Color expression may not be possible. The thickness of the coating film 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, as the thickness after drying. It is the following range.

[3-4] Drying of Coating Film Drying of the coating film after the colored resin composition is applied to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after predrying, it is again heated and dried. The conditions for the preliminary 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 the drying time are selected according to the type of solvent component, the performance of the dryer used, etc. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less.

  The temperature condition for reheating and drying is preferably a temperature higher than the preliminary drying temperature, specifically, usually 50 ° C. or more, preferably 70 ° C. or more, and usually 200 ° C. or less, preferably 160 ° C. or less, particularly preferably 130 It is the range below ° C. The drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes, depending on the heating temperature. The higher the drying temperature, the better the adhesion to the transparent substrate, but if it is too high, the binder resin may be decomposed to induce thermal polymerization to cause development failure. In addition, as a drying process of this coating film, you may use the pressure reduction drying method which dries in a pressure reduction chamber, without raising temperature.

[3-5] Exposure Step Image exposure is performed by overlapping a negative matrix pattern on a coating film of a colored resin composition and irradiating a light source of ultraviolet light or visible light through the mask pattern. Under the present circumstances, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen as needed, you may expose after forming oxygen blocking layers, such as a polyvinyl alcohol layer, on a photopolymerizable layer. The light source used for the above-mentioned image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, lamp light sources such as fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers and the like can be mentioned. An optical filter can also be used when irradiating and using the light of a specific wavelength.

[3-6] Development Step The color filter according to the present invention is an organic solvent or surfactant after image exposure is performed on the coating film using the colored resin composition according to the present invention by the above light source. By carrying out development using an aqueous solution containing H. and alkaline compounds, an image can be formed on a substrate and manufactured. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

  As the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium 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), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkyl benzene sulfonic acid Anionic surfactants such as salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, 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 may be used alone or in combination with the aqueous solution.
The conditions for the development processing are not particularly limited, but the development temperature is usually 10 ° C. or more, in particular 15 ° C. or more, further 20 ° C. or more, usually 50 ° C. or less, in particular 45 ° C. or less, further 40 ° C. or less Is preferred. The developing method can be any method such as immersion development, spray development, brush development, ultrasonic development and the like.

[3-7] Thermal Curing Treatment The color filter after development is subjected to a thermal curing treatment. The heat curing conditions at this time are selected in a temperature range of usually 100 ° C. or more, preferably 150 ° C. or more, and usually 280 ° C. or less, preferably 250 ° C. or less, and a time is 5 minutes or more and 60 minutes or less It is chosen in the range. The formation of a single-color patterning image is completed through these series of processes. This process is sequentially repeated to pattern black, red, green and blue to form a color filter. In addition, the order of patterning of four colors is not limited to the above-mentioned order.

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

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

[4-1] Liquid Crystal Display Device A method of 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, usually, an alignment film is formed on the color filter according to the present invention, and after spacers are dispersed on the alignment film, it is bonded to an opposing substrate to form a liquid crystal cell The liquid crystal is injected into the liquid crystal cell and connected to the opposite electrode to complete the process. The alignment film is preferably a resin film such as polyimide. For forming the alignment film, usually, a gravure printing method and / or a flexo printing method is adopted, and the thickness of the alignment film is several tens nm. After curing treatment of the alignment film by thermal baking, the alignment film is subjected to surface treatment by irradiation with ultraviolet light or treatment with a rubbing cloth to be processed into a surface state capable of adjusting the inclination of the liquid crystal.

  As the spacer, one having a size corresponding to the gap (gap) with the opposing substrate is used, and one having a size of 2 to 8 μm is usually preferable. It is also possible to form a transparent resin film photo spacer (PS) on the color filter substrate by photolithography and use it instead of the spacer. As a counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the opposite substrate is different depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm to 8 μm. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is 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 and then decompressed in a vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal, and then liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of pressure reduction 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 pressure reduction, and the heating temperature is usually in the range of 30 ° C. or more, preferably 50 ° C. or more, and usually 100 ° C. or less, preferably 90 ° C. or less.

The heating and holding 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. In the liquid crystal cell in which the liquid crystal is injected, the liquid crystal injection port is sealed by curing a UV curing resin, thereby completing a liquid crystal display (panel).
The type of liquid crystal is not particularly limited, and may be any conventionally known liquid crystal such as an aromatic, aliphatic or multicyclic compound, such as lyotropic liquid crystal or thermotropic liquid crystal. As thermotropic liquid crystals, nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, etc. are known, but any may be used.

[4-2] Organic EL Display Device In the case of producing an organic EL display device having a color filter of the present invention, for example, as shown in FIG. 1, the pixels 20 by the colored resin composition of the present invention Is stacked on the blue color filter on which the organic light emitting diode 500 is formed via the organic protective layer 30 and the inorganic oxide film 40, thereby producing a multicolor organic EL element.

  As a method of laminating the organic light emitting body 500, a method of sequentially forming the transparent anode 50, the hole injection layer 51, the hole transport layer 52, the light emitting layer 53, the electron injection layer 54, and the cathode 55 on the color filter The method of bonding the organic light-emitting body 500 formed on another substrate on the inorganic oxide film 40, etc. may be mentioned. The organic EL element 100 manufactured in this manner is applicable 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 more specifically described by way of synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the invention is not exceeded.

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

<Dispersant A: Dispersant "BYK-LPN6919" manufactured by BIC Chemie, Inc.>
A methacrylic acid-based AB block copolymer comprising an A block having hydrophilicity and a B block having a nitrogen atom-containing functional group. It has a repeating unit of following formula (2b) and (3b), and does not have a repeating unit of following formula (1b). The amine value is 120 mg KOH / g and the acid value is 1 mg KOH / g or less.

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

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

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

After maintaining the temperature at 110 ° C. for 3 hours, the separable flask was fitted with a gas inlet tube, and bubbling of a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine are charged in a reaction tank, and 110 ° C. Reaction for 9 hours.
It cooled to room temperature, and the weight average molecular weight Mw of polystyrene conversion measured by GPC obtained the binder resin A of 9,000 and an acid value of 101 mgKOH / g.

<Binder resin B>
The mixture was stirred and purged with nitrogen while 340.0 parts by mass of propylene glycol monomethyl ether acetate was heated to 120 ° C. To this, 10.4 parts by mass of styrene, 85.3 parts by mass of glycidyl methacrylate and 66.1 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are dropped, and the mixture is further stirred at 120 ° C. for 2 hours I kept doing it. Next, the inside of the reaction vessel was changed to air displacement, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 41.1 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 63.1 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the binder resin B thus obtained was about 8,000, and the acid value was 80 mg KOH / g.

<Binder resin C>
The temperature was raised to 120 ° C. while stirring with nitrogen substitution of 148.0 parts by mass of propylene glycol monomethyl ether acetate. Here, 7.3 parts by mass of styrene, 91.0 parts by mass of glycidyl methacrylate and 61.7 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are dropped and further stirred at 120 ° C. for 2 hours I kept doing it. Next, the inside of the reaction vessel was changed to air displacement, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.8 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Thereafter, 39.0 parts by mass of succinic anhydride and 0.7 parts by mass of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the binder resin B thus obtained was about 8,000, and the acid value was 88 mg KOH / g.

<Binder resin D>
While nitrogen-substituting, 190 parts by mass of propylene glycol monomethyl ether acetate and 190 parts by mass of propylene glycol monomethyl ether were stirred and heated to 120 ° C. Here, 3.5 parts by mass of benzyl methacrylate, 68.9 parts by mass of methacrylic acid and 39.7 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are dropped, and further 4 hours at 120 ° C. Stirring continued.

  After maintaining the temperature at 110 ° C. for 3 hours, the separable flask was fitted with a gas inlet tube, and bubbling of a mixed gas of oxygen / nitrogen = 5/95 (v / v) was started. Next, 52.7 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine are charged in a reaction tank, and 110 ° C. as it is. Reaction for 9 hours. The weight average molecular weight Mw in terms of polystyrene measured by GPC of the obtained binder resin D was about 9000, and the acid value was 146 mg KOH / g.

Preparation of Yellow Pigment Dispersion
C. I. 9.9 parts by mass of pigment yellow 138, 2.5 parts by mass of dispersant A in terms of solid content, 4.9 parts by mass of binder resin A in terms of solid content, and 82.7 parts of propylene glycol monomethyl ether acetate as a solvent A yellow pigment dispersion was prepared by charging 225 parts by mass of zirconia beads having a diameter of 0.5 mm in a stainless steel container and dispersing for 6 hours with a paint shaker.

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

<Photoinitiator A>
Oxime ester-based compound having the following chemical structure (4-acetoxyimino-5- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -5-oxopentanoate)

<Chain transfer agent A>
Pentaerythritol tetra (3-mercapto propionate) (made by Sakai Chemical Co., Ltd.)

<Surfactant A>
Megafuck F-559 (made by DIC Corporation)

<Preparation of Colored Resin Composition>
Each component described in Table 1 was mixed at a solid content ratio described in Table 1 to prepare a colored resin composition. Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used so that the total solid content of the colored resin composition would be 20.5% by mass. The mixing ratio (mass ratio) of PGMEA / PGME in the obtained colored resin composition was 90/10.

<Measurement of color characteristics>
The above colored resin composition was coated on a 50 mm square, 0.7 mm thick glass substrate (AN 100, manufactured by Asahi Glass Co., Ltd.) using a spin coater, and then dried at 80 ° C. for 3 minutes. Subsequently, the whole surface exposure processing was performed with the exposure amount of 100 mJ / cm < ² > with a 2 kW high pressure mercury lamp. Thereafter, development was carried out using a 0.1% by mass aqueous potassium hydroxide solution at a developer temperature of 23 ° C. Next, spray water-washing treatment was performed for 30 seconds under a water pressure of 3 kg / cm ² to prepare a colored resin composition coated substrate. Thereafter, a thermosetting treatment was carried out at 230 ° C. for 30 minutes to prepare a colored substrate. The transmission spectrum of the obtained colored substrate was measured by a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the luminance at the time when the chromaticity becomes sy = 0.607 with the SB2 light source is shown in Table 2.

From Table 2, it can be seen that the colored resin compositions of Examples 1 and 2 have higher luminance as compared to the colored resin composition of Comparative Example 1. Although the detailed mechanism of this effect is not clear, it is presumed that there are the following factors.
First, the binder resin contained in the colored resin composition of Comparative Example 1 does not contain the repeating unit represented by the above general formula (I), but contains the repeating unit derived from (meth) acrylic acid. A hydrogen bond is strongly formed between carboxy groups contained in the repeating unit derived from (meth) acrylic acid, and the carboxy group is disposed on the inner side of the resin molecule, and the carboxy group and the phthalocyanine compound mutually It is considered that the action became weak and the decomposition reaction of the phthalocyanine compound (1) proceeded during the heat curing treatment to lower the luminance.

  On the other hand, the binder resin contained in the colored resin composition of Examples 1 and 2 contains the repeating unit represented by the general formula (I), and the carboxy group contained therein is sufficiently from the main chain It is considered that it is difficult to form a strong hydrogen bond between carboxy groups because of high flexibility because they are separated. As a result, a carboxy group is easily disposed on the outside of the resin molecule, and a bond is formed between the central metal site or the like in the phthalocyanine compound (1) and the carboxy group, and the resin covers the phthalocyanine compound (1). It is considered that the decomposition reaction of the phthalocyanine compound (1) at the time of the heat curing treatment was inhibited, resulting in high brightness.

Claims (4)

A colored resin composition comprising (A) a colorant, (B) a solvent, (C) a binder resin, and (D) a photopolymerization initiator,
The (A) coloring agent includes a phthalocyanine compound having a chemical structure represented by the following general formula (1),
Colored resin composition characterized by said (C) binder resin containing binder resin (c-1) which has a repeating unit represented by following General formula (I).

(In formula (1), each of A ^{1 to} A ¹⁶ independently represents a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), provided that one or more of A ^{1 to} A ¹⁶ are used. Represents a group represented by the following general formula (2))

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

(In formula (I), R ¹ represents a hydrogen atom or a methyl group.
R ² represents a trivalent hydrocarbon group which may have a substituent.
R ³ represents a hydrogen atom or a methyl group.
R ⁴ represents a divalent hydrocarbon group which may have a substituent. )   The colored resin composition according to claim 1, wherein the (A) colorant further comprises a pigment.   The color filter which has a pixel produced using the coloring resin composition of Claim 1 or 2.   An image display apparatus comprising the color filter according to claim 3.

Images