JP7003637B2 - Colored resin composition, color filter, and image display device - Google Patents

Description

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

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

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

Japanese Unexamined Patent Publication No. 2009-051896 International Publication No. 2004/157387

As a result of the study by the present inventor, it was found that the brightness of the obtained color filter is not practically sufficient in the colored resin compositions described in Patent Document 1 and Patent Document 2.
Therefore, an object of the present invention is to provide a colored resin composition capable of obtaining a color filter having a practically sufficient luminance.

As a result of diligent studies by the present inventor, it has been found that the above-mentioned 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. rice field.
That is, the present invention has the following configurations [1] to [4].

[1] A colored resin composition containing (A) a colorant, (B) a solvent, (C) a binder resin, and (D) a photopolymerization initiator.
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
A colored resin composition, wherein the binder resin (C) contains a binder resin (c-1) having a repeating unit represented by the following general formula (I).

(In the formula (1), A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2), but one or more of A ¹ to A ¹⁶ . Represents a group represented by the following general formula (2).)

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

(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 colorant (A) further contains a pigment.
[3] A color filter having pixels created by using the colored resin composition according to [1] or [2].
[4] An image display device having the color filter according to [3].

According to the present invention, it is possible to provide a colored resin composition capable of obtaining a color filter having practically sufficient brightness.

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

Hereinafter, the constituent requirements and the like of the present invention will be described in detail, but these are examples of embodiments of the present invention and are not limited to these contents.
In addition, "(meth) acrylic", "(meth) acrylate" and the like mean "acrylic and / or methacrylic", "acrylate and / or methacrylate" and the like, for example, "(meth) acrylic acid" is "(meth) acrylic acid". It shall mean "acrylic acid and / or methacrylic acid". Further, the "total solid content" means all the components other than the solvent component described later, which are contained in the pigment dispersion liquid or the colored resin composition.

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

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

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

In the formula (1), A ¹ to A ¹⁶ independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

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

When the (A) colorant contained in the colored resin composition of the present invention contains the phthalocyanine compound (1), the brightness of the obtained color filter is increased. Although the detailed mechanism has not been clarified, the phthalocyanine compound (1) has a group represented by the general formula (2) in the phthalocyanine skeleton, which makes it soluble in a solvent and at the time of baking the general formula (2). It is considered that the heat resistance is dramatically improved and the brightness is increased even after baking by pigmenting and suppressing the decomposition by the π-π interaction between) and the π-π interaction between the phthalocyanine skeletons.

(A ¹ to A ¹⁶ )
In the above formula (1), A ¹ to A ¹⁶ independently represent a hydrogen atom, a halogen atom, or a group represented by the following general formula (2). However, one or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2).

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

Examples of the halogen atom in A ¹ to A ¹⁶ include a fluorine atom, a chlorine atom, a bromine atom and the like, and the fluorine atom is preferable from the viewpoint of adjusting to the optimum hue as a green dye used in a color filter.

(X)
X in the general formula (2) represents a divalent linking group. The divalent linking group is not particularly limited, and examples thereof include an oxygen atom, a sulfur atom, and an —N (R ^a1 ) — group. R ^a1 represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Among these, 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) when it is made into a colored resin composition, and oxygen is preferable. Atoms are more preferred.

(Substituents that the benzene ring may have)
Further, the benzene ring in the formula (2) may have an arbitrary substituent. The substituent is not particularly limited, but is a halogen atom, an alkyl group, an alkoxy group (-OR ^A group (where ^RA represents an alkyl group)), an alkoxycarbonyl group (-COOR ^A group (where ^RA )). Represents an alkyl group))), an aryl group, an aryloxy group (-OR ^B group (where RB represents an aryl group)), an aryloxycarbonyl ^{group (-COOR B group} (where RB represents an aryl ^group )). (Representing a group))) may be mentioned, and the alkyl group ( ^-RA group) and the aryl group ( ^-RB group) contained in these groups may be further substituted with these substituents. Among these, an alkoxycarbonyl group is preferable from the viewpoint of solubility in a solvent and formation of a hydrogen bond with the binder resin (c-1) when the colored resin composition is formed.

The alkyl group contained in these groups may be linear, branched, or cyclic, but may be soluble in a solvent and may be used with the binder resin (c-1) in the form of a colored resin composition. It is preferably linear from the viewpoint of suppressing the inhibition of hydrogen bond formation.
The number of carbon atoms of the alkyl group is not particularly limited, but is usually preferably 1 or more, 2 or more, preferably 6 or less, more preferably 5 or less, still more preferably 4 or less. When it is at least the above lower limit value, the solubility of the phthalocyanine compound (1) in the solvent tends to be improved, and when it is at least the above upper limit value, a hydrogen bond with the binder resin (c-1) is formed. Tends to be easy to do.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and the like, and from the viewpoint of suppressing 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.

Further, the aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
The number of carbon atoms of the aryl group is not particularly limited, but is usually preferably 4 or more and 6 or more, preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. When it is at least the above lower limit value, the solubility of the phthalocyanine compound (1) in the solvent tends to be improved, and when it is at least the above upper limit value, a hydrogen bond with the binder resin (c-1) is formed. Tends to be easy to do.

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

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

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

As a method for producing the phthalocyanine compound (1), a known method can be adopted, and for example, the method described in JP-A No. 05-345861 can be adopted.

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

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

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

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

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

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

The content ratio of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, and 10% by mass with respect to 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 further preferable, 30% by mass or less is further preferable, and 25% by mass or less. Is particularly preferable. When it is set to the lower limit value or more, the color characteristics such as luminance tend to be improved, and when it is set to the upper limit value or less, the deterioration of pattern formation at the time of creating a color filter tends to be suppressed.

When other colorants are contained, the content ratio thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, based on the total solid content of the colored resin composition. 10% by mass or more is more preferable, 15% by mass or more is particularly preferable, 40% by mass or less is more preferable, 35% by mass or less is more preferable, 30% by mass or less is further preferable, and 25% by mass or less is particularly preferable. When it is set to the lower limit value or more, thermal decomposition during hot firing during color filter production tends to be suppressed, and when it is set to the upper limit value or less, pattern formation deterioration during color filter production tends to be suppressed. There is.

[1-2] (B) Solvent (B) Solvent has the function of dissolving or dispersing a colorant, a binder resin, a photopolymerization initiator, and other components in the colored resin composition of the present invention to adjust the viscosity. Have.
The solvent (B) may be any solvent that can dissolve or disperse each component.

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

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

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, diamil ether, ethylisobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

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

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

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

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

It is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. The combined use of such a high boiling point solvent makes it difficult for the colored resin composition to dry, but has the effect of making it difficult for the pigment dispersion liquid to break the mutual relationship due to rapid drying. The content ratio of the high boiling point solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass with respect to the solvent (B). By setting it to the above lower limit value or more, for example, it tends to be easy to prevent colorant components and the like from precipitating and solidifying at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the composition It tends to avoid slowing down the drying process and causing problems such as poor tact in the vacuum drying process and pin marks on the prebake.
The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher.
As a preferable high boiling solvent, for example, among the above-mentioned various solvents, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanoldi Examples include acetate and triacetin.

When the pixels of the color filter are formed by the inkjet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is suitable. When it is at least the above lower limit value, the uniformity of the obtained coating film tends to be good, and when it is at least the above upper limit value, there is a tendency that the residual solvent at the time of firing is easily reduced.
Further, from the viewpoint of the uniformity of the obtained coating film, the vapor pressure of the solvent can be usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less.

In the manufacture of color filters by the inkjet method, the ink emitted from the nozzles is extremely fine, ranging from several to several tens of pL, so the solvent evaporates and the ink concentrates before landing around the nozzle opening or in the pixel bank.・ Tends to dry out. In order to avoid this, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable to contain a solvent having a boiling point of 180 ° C. or higher. It contains a solvent having a boiling point of 200 ° C. or higher, more preferably 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more, more preferably 70% by mass or more, and most preferably 90% by mass or more in the total solvent contained in the colored resin composition. By setting the value to the lower limit or more, the effect of preventing evaporation of the solvent from the droplets tends to be sufficiently exhibited.

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

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

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

[1-3] (C) Binder Resin The colored resin composition of the present invention contains (C) a binder resin. (C) By containing the binder resin, it is possible to achieve both film curability by photopolymerization and solubility by a developing solution.
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)”). In some cases).

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.

Although the colored resin composition of the present invention contains the binder resin (c-1), the carboxy group in the repeating unit represented by the general formula (I) is sufficiently separated from the main chain and has high flexibility. , The carboxy groups are likely to be arranged so as to be exposed to the outside of the resin molecule without forming a strong hydrogen bond. A bond such as a hydrogen bond is formed between the central metal moiety and the ether bond moiety in the phthalocyanine compound (1) and the carboxy group of the binder resin (c-1), and the phthalocyanine compound (1) is covered with the resin. It is considered that the decomposition reaction of the phthalocyanine compound (1) during the thermosetting treatment is inhibited, resulting in high brightness.

(R ² )
In formula (I), R ² represents a trivalent hydrocarbon group which may have a substituent. Examples of the trivalent hydrocarbon include a trivalent aliphatic hydrocarbon group.
Examples of the trivalent aliphatic hydrocarbon group include a linear group, a branched chain group, a cyclic group, and a combination thereof.
The number of carbon atoms of the trivalent aliphatic hydrocarbon group is not particularly limited, but is usually 1 or more, 2 or more, more preferably 3 or more, usually 15 or less, 10 or less, more preferably 8 or less, and 5 The following is more preferable. Within the above range, hydrogen bonds with the phthalocyanine compound (1) are likely to be formed, and the brightness tends to be improved.
Specific examples of the trivalent aliphatic hydrocarbon group include the following.

Examples of the substituent that 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. Examples of the divalent hydrocarbon include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon ring group.
Examples of the divalent aliphatic hydrocarbon group include a linear group, a branched chain group, a cyclic group, and a combination thereof.
The number of carbon atoms of the divalent aliphatic hydrocarbon group is not particularly limited, but usually 1 or more, 2 or more is preferable, 3 or more is more preferable, 4 or more is particularly preferable, and usually 15 or less, 10 or less is preferable, and 8 The following is more preferable, and 6 or less is further preferable. When it is at least the above lower limit value, hydrogen bonds between the phthalocyanine compound (1) and the carboxy group of the binder resin (c-1) tend to be formed strongly, and when it is at least the above upper limit value, the phthalocyanine compound tends 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 an ethylene group, a propylene group, an ethenylene group, a cyclohexa-4-ene-1,2-diyl group, a cyclohexa-1,2-diyl group and the like. Among these, an ethylene group, an ethenylene group, and a cyclohexa-4-ene-1,2-diyl group are preferable from the viewpoint of promoting hydrogen bond formation with the carboxy group of the binder resin (c-1).

On the other hand, the number of carbon atoms of the divalent aromatic hydrocarbon ring group is not particularly limited, but is usually preferably 6 or more, and preferably 12 or less. When it is at least the above lower limit value, it tends to promote the π-π interaction with the phthalocyanine compound (1), and when it is at least the above upper limit value, it is in the process of manufacturing the color filter of the binder resin (c-1). There is a tendency that the decrease in brightness due to yellowing during firing can be suppressed.

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

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

The binder resin (c-1) has a repeating unit represented by the general formula (I), but may further contain other repeating units.
Other repeating units are 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 producing a color filter by an 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 , the one mentioned in R ² can be preferably applied.

Further, as the other repeating unit, the repeating unit represented by the following general formula (III) is preferable from the viewpoint of suppressing yellowing during hot firing in the color filter manufacturing step.

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.
Examples of the monovalent hydrocarbon group include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon ring group.

Examples of the monovalent aliphatic hydrocarbon group include a linear group, a branched chain group, a cyclic group, and a combination thereof.
The number of carbon atoms of the monovalent aliphatic hydrocarbon group is not particularly limited, but usually 1 or more, 2 or more is preferable, 3 or more is more preferable, 5 or more is more preferable, 7 or more is particularly preferable, and usually 20 or less and 18 or less. Is preferable, 15 or less is more preferable, and 12 or less is further preferable. When it is set to the lower limit value or more, yellowing during hot firing in the color filter manufacturing step tends to be suppressed, and when it is set to the upper limit value or less, the alkaline developability at the time of manufacturing the color filter tends to be improved. ..
Specific examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a tetrahydrodicyclopentadienyl group, a cyclohexyl group and the like. Among these, a methyl group or a tetrahydrodicyclopentadienyl group is preferable from the viewpoint of suppressing yellowing due to heat.

The number of carbon atoms of the monovalent aromatic hydrocarbon group is not particularly limited, but is preferably 6 or more, and preferably 12 or less. When it is at least the above lower limit value, it tends to promote the π-π interaction with the phthalocyanine compound (1), and when it is at least the above upper limit value, the brightness is lowered due to yellowing during firing in the color filter manufacturing process. Tends to be suppressed.

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

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

Further, as the other repeating unit, the 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.

The content ratio of the repeating unit represented by the general formula (I) contained in the binder resin (c-1) is not particularly limited, but is preferably 15 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. Preferably, 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 further preferable, 50 mol% or less is further preferable, and 45 mol% or less is preferable. Is particularly preferable. When it is at least the above lower limit value, the alkali developability is improved and hydrogen bonds with the phthalocyanine compound (1) tend to be strongly formed, and when it is at least the above upper limit value, the resin itself is thermally decomposed. Tends to be suppressed.

When the binder resin (c-1) contains a repeating unit represented by the general formula (II), the content ratio thereof is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and 12 mol% or more. Further, 15 mol% or more is further 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 further preferable, and 30 mol% or less is particularly preferable. When the value is equal to or higher than the lower limit, 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) during hot firing. There is a tendency that the above-mentioned upper limit value or less is suppressed, and that the shape at the time of pixel formation at the time of patterning is suppressed from being deteriorated due to excessive curing at the time of exposure.

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

When the binder resin (c-1) contains a repeating unit represented by the general formula (IV), the content ratio thereof is not particularly limited, but is preferably 2 mol% or more, more preferably 3 mol% or more, and 4 mol% or more. Further, 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 further preferable, and 12 mol% or less is particularly preferable. By setting the value to the lower limit or higher, the π-π interaction with the phthalocyanine compound (1) tends to be promoted and the thermal decomposition of the phthalocyanine compound (1) tends to be suppressed, and by setting the value to the upper limit or lower. Yellowing due to thermal decomposition of the resin itself tends to be suppressed.

The method for producing the binder resin (c-1) is not particularly limited. For example, for a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the epoxy contained in the copolymer is used. 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. Specifically, the production method described in JP-A-2009-053652 can be adopted.

The binder resin (C) in the colored resin composition of the present invention contains the binder resin (c-1), but may further contain other binder resin (c-2).
The other binder resin (c-2) can be used without particular limitation as long as it exhibits the function as a binder resin, and is described in International Publication No. 2016/158668 [1-]. 6-2] A linear alkali-soluble resin containing a carboxy group in the main chain, [1-6-3] a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxy group portion of the carboxy group-containing resin, [1-6-3]. 1-6-4] (meth) acrylic resin, [1-6-5] epoxy (meth) acrylate resin having a carboxy group, and JP-A-2012-018374 and JP-A-2012-404365. Examples thereof include a resin having a side chain containing a cyclic ether group.

In the colored resin composition of the present invention, the content ratio of the binder resin (C) is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, and 10% by mass, based on the total solid content of the colored resin composition. It is more preferably mass% or more, further preferably 12% by mass or more, particularly preferably 15% by mass or more, still preferably 50% by mass or less, further preferably 40% by mass or less, further preferably 30% by mass or less, and 25% by mass. More preferably, it is more preferably mass% or less, and particularly preferably 20% by mass or less. Within the above range, alkali developability and patterning after firing tend to be good.

In the colored resin composition of the present invention, the content ratio of the binder resin (c-1) 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. Preferably, 3% by mass or more is further preferable, 4% by mass or more is further preferable, 5% by mass or more is particularly preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is further preferable. It is preferable, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. By setting the value to the lower limit or higher, the phthalocyanine compound (1) and the binder resin (c-1) form hydrogen bonds, which tends to increase the ability to suppress thermal decomposition during baking, and the value should be set to the upper limit or lower. The content ratio of other polymerized components is relatively high, and the deterioration of the patterning shape during development tends to be suppressed.

Further, the content ratio of the binder resin (c-1) in the (C) binder resin of the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass. The above is further preferable, 20% by mass or more is further preferable, 25% by mass or more is particularly preferable, 30% by mass or more is most preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, and 50% by mass is 50% by mass. The following is more preferable, and 40% by mass or less is particularly preferable. Within the above range, the amount of hydrogen bonds between the phthalocyanine compound (1) and the binder resin (c-1) tends to be appropriate, and the ability to suppress thermal decomposition during baking tends to be high.

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

Examples of the photopolymerization initiator include a metallocene compound containing a titanosen compound described in JP-A-59-152396 and JP-A-61-151197, and a hexaarylbiimidazole described in JP-A No. 10-39503. Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical initiators such as N-aryl-α-amino acid esters, α- Examples thereof include aminoalkylphenone-based compounds, oxime ester-based initiators described in JP-A-2000-80068, and the like.

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

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

Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p) -Isopropylphenyl) Ketone, 1-Hydroxy-1- (p-dodecylphenyl) Ketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 1,1,1 -Acetophenone derivatives such as trichloromethyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;

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

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

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

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

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

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

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

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

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

The carbon number of the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, more preferably, 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 ethiloyl group, a propanoyl group, a butanoyl group and the like.
Examples of the substituent that the alkanoyl group may have include an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group and the like, and the substituent is not substituted from the viewpoint of easiness of synthesis. Is preferable.

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

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

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

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

The carbon number of the allylloyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. It is preferably 10 or less, more preferably 9 or less. Specific examples of the allylloyl group include a benzoyl group and a naphthoyl group.
Examples of the substituent that the allylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and from the viewpoint of easiness of synthesis, an ethyl group is used. Is preferable.

The number of carbon atoms of the heteroarylloyl group in R ^23a is not particularly limited, but from the viewpoint of solubility in a solvent, it is usually 7 or more, preferably 8 or more, more preferably 9 or more, and usually 20 or less, preferably 15 or less. , More preferably 10 or less, still more preferably 9 or less. Specific examples of the heteroaryl group include a fluorobenzoyl group, a chlorobenzoyl group, a bromobenzoyl group, a fluoronaphthoyl group, a chloronaphthoyl group, a bromonaphthoyl group and the like.
Examples of the substituent that the heteroarylloyl group may have include a carbonyl group, a carboxy group, a hydroxyl group, a phenyl group, a benzyl group, a cyclohexyl group, a nitro group and the like, and there is no such group from the viewpoint of ease of synthesis. It is preferably a substitution.
Among these, 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.

Commercially available products of such oxime ester compounds include OXE-02 and OXE-03 manufactured by BASF, TR-PBG-304, TR-PBG-314 manufactured by Changshu Power Electronics Co., Ltd., and N-1919 manufactured by ADEKA Corporation. There are NCI-930, NCI-831 and the like.

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

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

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

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

Of these, 2-mercaptobenzothiazole and 2-mercaptobenzoimidazole are preferable among the mercapto group-containing compounds having an aromatic ring, and trimethylolpropanthris (3-) among the aliphatic mercapto group-containing compounds is preferable. Mercaptopropionate), Pentaerythritol tetrakis (3-mercaptopropionate), Pentaerythritoltris (3-mercaptopropionate), Trimethylol propanthris (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptobuty) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trion is preferred.

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

In the colored resin composition of the present invention, the content ratio of the (D) photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, based on the total solid content of the colored resin composition. 4, 4% by mass or more is further preferable, 6% by mass or more is particularly preferable, 15% by mass or less is more preferable, 12% by mass or less is more preferable, 10% by mass or less is further preferable, and 9% by mass or less is particularly preferable. When the value is equal to or higher than the lower limit, the patterning characteristics after development tend to be ensured, and when the value is equal to or higher than the upper limit, 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 is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total solid content of the colored resin composition. Is more preferable, 0.2% by mass or more is further preferable, 0.3% by mass or more is particularly preferable, 5% by mass or less is preferable, 2% by mass or less is more preferable, 1% by mass or less is further preferable, and 0. 6% by mass or less is particularly preferable. Within the above range, storage stability and patterning forming ability during alkaline development tend to be ensured.

[1-5] Other solids The colored resin composition of the present invention may further contain solids other than the above components, if necessary. Examples of such a component include a photopolymerizable monomer, a dispersant, a dispersion aid, a surfactant 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 is an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, (Refered to be "ethylenic compound") is preferable. The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized by the action of a photopolymerization initiator and cured. The monomer in the present invention means a concept opposite to a so-called polymer substance, and means a concept containing a dimer, a trimer, and an oligomer in addition to the monomer in a narrow sense.
In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds contained in the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 5 or more. The number is 8 or less, more preferably 7 or less. When it is at least the lower limit value, the sensitivity tends to be high, and when it is at least the upper limit value, the solubility in a solvent tends to be improved.

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

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

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

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

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

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

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

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

The content 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, based on 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 30% by mass or less. The ratio of (A) the colorant to 100 parts by mass 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. As mentioned above, it is particularly preferably 60 parts by mass or more, usually 200 parts by mass or less, preferably 100 parts by mass or less, and further preferably 80 parts by mass or less.

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

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

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

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

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

The 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. It is preferably 8 or less, and more preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthrasenyl group and the like, and among these, a phenyl group, a methylphenyl group and an ethylphenyl group. , Dimethylphenyl group, or diethylphenyl group, more preferably phenyl group, methylphenyl group, or ethylphenyl group.

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

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

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

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

These cyclic structures may further have substituents.

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

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

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

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

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

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

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

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

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

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

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

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

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group or a phenylmethylene group.
Examples of the substituent that the alkyl group may have in R ⁸ include a halogen atom and an alkoxy group. Further, examples of the substituent that the aryl group or the aralkyl group may have include a chain-like alkyl group, a halogen atom, an alkoxy group and the like. Further, the chain-like alkyl group represented by R ⁸ includes both a linear chain and a branched chain.

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

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

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

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

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

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

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

The molecular weight of the block copolymer is preferably in the range of 1000 to 30,000 in terms of polystyrene-equivalent weight average molecular weight (hereinafter, may be referred to as “Mw”). When it is within the above range, the dispersion stability is good, and dry foreign matter tends to be less likely to be generated during coating by the slit nozzle method.

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

When the colored resin composition of the present invention contains a pigment and a dispersant, the content ratio of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 0.5 parts by mass or more, based on 100 parts by mass of the pigment. Is 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 70 parts by mass or less, more preferably 50 parts by mass or less. It is more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. Within the above range, there is a tendency that a colorable resin composition having excellent dispersion stability and high brightness can 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 in order to improve the dispersibility of the pigment and the dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrone, perylene, perinone, and diketopyrrolop. Examples thereof include derivatives such as pyrrol-based and dioxazine-based pigments. As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group and the like are directly on the pigment skeleton or an alkyl group, an aryl group or a complex. Examples thereof include those bonded via a ring group and the like, preferably a sulfonic amide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. Further, these substituents may be substituted in a plurality of one pigment skeleton, or may be a mixture of compounds having different numbers of substitutions. Specific examples of the pigment derivative include azo pigment sulfonic acid derivative, phthalocyanine pigment sulfonic acid derivative, quinophthalone pigment sulfonic acid derivative, isoindrin pigment sulfonic acid derivative, anthraquinone pigment sulfonic acid derivative, and quinacridone pigment sulfonic acid derivative. Examples thereof include a sulfonic acid derivative of a diketopyrrolopyrrole pigment and a sulfonic acid derivative of a dioxazine pigment.

[1-5-3] Surfactant As the surfactant, various substances such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but they may adversely affect various properties. It is preferable to use a nonionic surfactant because of its low value. The content ratio of the surfactant is usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0, based on the total solid content of the colored resin composition. It is used in the range of 1% by mass or more, usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and most preferably 0.3% by mass or less.

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

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

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

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

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

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

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

For the transparent substrate and the black matrix-forming substrate, in order to improve the surface physical properties such as adhesiveness, corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. are required. May be done. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When the thin film forming treatment of various resins is performed, the film thickness is usually 0.01 μm or more, preferably 0.05 μm or more, and usually 10 μm or less, preferably 5 μm or less.

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

The black matrix is formed on a transparent substrate by using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, a nickel-tungsten alloy, or the like is used, and these may be laminated in a plurality of layers.
These metal light-shielding films are generally formed by an etching method, and after forming a desired pattern in a film shape by a positive photoresist, dicerium ammonium nitrate and perchloric acid and / or nitric acid are added to chromium. A black matrix is formed by using an etching solution mixed with the above, and for other materials, it is carved using an etching solution suitable for the material, and finally the positive photoresist is peeled off 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 a vapor deposition method or a sputtering method. Next, after forming a coating film of the colored resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

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

[3-3] Pixel formation The pixel formation method differs depending on the type of the colored resin composition used, but here, a case where a photopolymerizable composition is used as the colored resin composition will be described as an example.
A colored resin composition of one color of red, green, and blue is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is placed on the coating film, and image exposure is performed via this photomask. A pixel image is formed by development and, if necessary, heat curing or photocuring. By performing this operation for each of the three colored resin compositions of red, green, and blue, a color filter image can be formed.

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

If the thickness of the coating film is too large, it may be difficult to develop the pattern and it may be difficult to adjust the gap in the liquid crystal cell formation process, while if it is too small, it is difficult to increase the pigment concentration, which is desired. Color development may be impossible. The thickness of the coating film after drying is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm. The range is as follows.

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

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

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

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

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

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

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

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

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

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

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

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

The gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. .. The degree of decompression in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ^-3 or more, and usually 1 × 10 ^-7 Pa or less, preferably 1 × 10 ^-6 Pa or less. .. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually in the range of 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower.

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

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

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

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

<Parthalocyanine compound A>
A phthalocyanine compound A having the following chemical structure synthesized based on Example 30 of JP-A No. 05-345861 was used.

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

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

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

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

After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts by mass of glycidyl methacrylate, 0.4 parts by mass of 2,2'-methylenebis (4-methyl-6-t-butylphenol), and 0.8 parts by mass of triethylamine were charged in the reaction vessel, and the temperature was 110 ° C. as it was. Was reacted for 9 hours.
After cooling to room temperature, a binder resin A having a polystyrene-equivalent weight average molecular weight Mw of 9000 and an acid value of 101 mgKOH / g measured by GPC was obtained.

<Binder resin B>
340.0 parts by mass of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. 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 were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Continued to do. Next, the inside of the reaction vessel was replaced with air, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 41.1 parts by mass of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 63.1 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the mixture was reacted at 120 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the binder resin B thus obtained was about 8000, and the acid value was 80 mgKOH / g.

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

<Binder resin D>
190 parts by mass of propylene glycol monomethyl ether acetate and 190 parts by mass of propylene glycol monomethyl ether were stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. 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 were added dropwise thereto, and the mixture was further added at 120 ° C. for 4 hours. Continued to stir.

After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 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 were charged in the reaction vessel, and the temperature was 110 ° C. as it was. Was reacted for 9 hours. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the obtained binder resin D was about 9000, and the acid value was 146 mgKOH / g.

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

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

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

<Chain transfer agent A>
Pentaerythritol Tetra (3-Mercaptopropionate) (manufactured by Yodo Kagaku Co., Ltd.)

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

<Preparation of colored resin composition>
Each component shown in Table 1 was mixed at the solid content ratio shown in Table 1 to prepare a colored resin composition. Propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) were used so that the total solid content of the colored resin composition was 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 colored resin composition was applied on a 50 mm square, 0.7 mm thick glass substrate (AN100 manufactured by Asahi Glass Co., Ltd.) with a spin coater, and then dried at 80 ° C. for 3 minutes. Next, a full-scale exposure process was performed with an exposure amount of 100 mJ / cm ² using a 2 kW high-pressure mercury lamp. Then, the development treatment was carried out using a 0.1 mass% potassium hydroxide aqueous solution at a developer temperature of 23 ° C. Next, a spray water washing treatment was performed at a water pressure of 3 kg / cm ² for 30 seconds to prepare a colored resin composition-coated substrate. Then, the thermosetting treatment was performed at 230 ° C. for 30 minutes to prepare a colored substrate. Table 2 shows the luminance of the obtained colored substrate when the transmission spectrum was measured by a spectrophotometer U-3310 manufactured by Hitachi, Ltd. and the chromaticity was sy = 0.607 with an SB2 light source.

From Table 2, it can be seen that the colored resin compositions of Examples 1 and 2 have higher brightness than the colored resin compositions of Comparative Example 1. The detailed mechanism of this effect has not been clarified, but 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 general formula (I), while containing the repeating unit derived from (meth) acrylic acid. Hydrogen bonds are strongly formed between the carboxy groups contained in the repeating unit derived from the (meth) acrylic acid, and the carboxy groups are arranged inside the resin molecule, and the carboxy groups and the phthalocyanine compound interact with each other. It is probable that the action was weakened and the decomposition reaction of the phthalocyanine compound (1) proceeded during the thermosetting treatment to lower the brightness.

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

Claims (6)

A colored resin composition containing (A) a colorant, (B) a solvent, (C) a binder resin, and (D) a photopolymerization initiator.
The colorant (A) contains a phthalocyanine compound having a chemical structure represented by the following general formula (1).
A colored resin composition, wherein the binder resin (C) contains a binder resin (c-1) having a repeating unit represented by the following general formula (I).

(In the formula (1), A ¹ to A ¹⁶ are independently hydrogen atoms, halogen atoms, or the following general formulas (
Represents the group represented by 2). However, one or more of A ¹ to A ¹⁶ represents a group represented by the following general formula (2). )

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

(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.
^R4 represents a divalent hydrocarbon group which may have a substituent. ) In the above formula (1), A ¹ ~ A ¹⁶ In claim 1, the halogen atom in the above is a fluorine atom.
The colored resin composition according to the above. Claimed that the benzene ring in the formula (2) has an alkoxycarbonyl group as a substituent.
Item 2. The colored resin composition according to Item 1 or 2. The colored resin composition according to any one of claims 1 to 3 , wherein the colorant (A) further contains a pigment. A pixel having a pixel produced by using the colored resin composition according to any one of claims 1 to 4 .
Color filter. An image display device having the color filter according to claim 5 .

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