JP7159948B2 - Colored resin composition, color filter, and image display device - Google Patents

Description

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

2. Description of the Related Art Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for manufacturing color filters used in liquid crystal display devices and the like. Among them, the pigment dispersion method, which has excellent characteristics on average, is most widely used from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, and the like.

In recent years, color filters are required to have higher brightness, higher contrast, and a wider color gamut. Pigments are generally used as colorants for determining the color of color filters from the viewpoint of heat resistance and light resistance. The use of dyes instead of pigments as materials has been extensively studied. As for the green pixel, the use of a specific phthalocyanine compound as a dye is being investigated (see, for example, Patent Documents 1 and 2).

JP 2014-043556 A JP 2015-072440 A

As a result of investigations by the present inventors, it was found that the color resin composition described in Patent Document 1 does not provide practically sufficient contrast in the resulting color filter. On the other hand, with the colored resin composition described in Patent Document 2, it was found that the brightness of the resulting color filter was not practically sufficient.
Accordingly, an object of the present invention is to provide a colored resin composition capable of forming a pattern with practically sufficient contrast and brightness.

As a result of intensive studies by the present inventors, it was found that the above problems can be solved by using a specific phthalocyanine compound as a coloring agent and a specific photopolymerization initiator as a photopolymerization initiator. , led to the present invention.
That is, the present invention has the following configurations [1] to [5].

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

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

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

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

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

(In formula (I), R ^d1 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ^d2 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
p represents 0 or 1;
R ^d3 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3;
R ^d4 and R ^d5 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group. R ^d4 and R ^d5 may combine with each other to form a ring. )

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

ADVANTAGE OF THE INVENTION According to this invention, the contrast and brightness|luminance can provide the colored resin composition which can form a practically sufficient pattern.

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

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

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

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

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

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

The (A) colorant contained in the colored resin composition of the present invention contains a phthalocyanine compound (1), and the phthalocyanine compound (1) is a π-π interaction between phthalocyanine rings, represented by the general formula (2). Due to the π-π interaction between the groups that are formed, the molecules easily associate with each other. In addition, having a fluorine atom with a small atomic radius makes the packing between the molecules more dense, and the formation of an association between two molecules increases the brightness. It is considered to be.

On the other hand, the phthalocyanine compound (1) is not limited to association formation between two molecules due to intermolecular π-π interaction and the like, and the association progresses further to easily form aggregates. It is thought that light scattering tends to lower the contrast.

Therefore, in the colored resin composition of the present invention, by including a photopolymerization initiator having a fluorene skeleton, due to the π-π interaction between the fluorene skeleton and the phthalocyanine ring, bimolecular Although the formation of aggregates is promoted, the formation of aggregates due to excessive association is suppressed, light scattering is less likely to occur, and contrast reduction can be suppressed. At this time, it is considered that the aromatic hydrocarbon ring skeleton interacts more easily with the electron-rich phthalocyanine skeleton than the aromatic heterocyclic ring skeleton due to the charge transfer effect.

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

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

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

(Substituent that the benzene ring may have)
Moreover, the benzene ring in formula (2) may have an arbitrary substituent. The substituent is not particularly limited, but 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)), aryl group, aryloxy group (-OR ^B group (where RB represents an aryl group)), aryloxycarbonyl ^{group (-COOR B group (} where RB represents an aryl )), and the alkyl group (-R ^A group) or aryl group (-R ^B 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 luminance.

The alkyl group contained in these groups may be linear, branched, or cyclic, but is preferably linear from the viewpoint of solubility in solvents and brightness.
Although the number of carbon atoms in the alkyl group is not particularly limited, it is generally preferably 1 or more and 2 or more, preferably 6 or less, more preferably 5 or less, and still more preferably 4 or less. When the lower limit value or more is used, the lipophilicity tends to be improved, and the solubility of the phthalocyanine compound (1) in a solvent tends to be improved. It does not inhibit the π interaction and tends to increase the brightness by forming an aggregate between two molecules.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and the like. From the viewpoint of solubility in a solvent and brightness, a methyl group or an ethyl group is preferable, and an ethyl group. is more preferred.

Moreover, the aryl group contained in these groups may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group.
Although the number of carbon atoms in the aryl group is not particularly limited, it is generally preferably 4 or more and 6 or more, preferably 12 or less, more preferably 10 or less, and even more preferably 8 or less. When it is at least the above lower limit, the solubility of the phthalocyanine compound (1) in a solvent tends to be improved, and when it is at most the above upper limit, hue change due to the aryl group tends to be suppressed.

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

When the benzene ring in formula (2) has an optional substituent, the number of substituents is not particularly limited. From the viewpoint of improving brightness by forming an association between two molecules, the number of substitutions is preferably one per one benzene ring.
Further, when the benzene ring in formula (2) has an optional substituent, the substitution position may be o-position, m-position, or p-position, but the phthalocyanine compound derived from the symmetry of the molecule The p-position is preferred from the viewpoint of improvement in brightness due to association formation between two molecules in (1).

At least one of A ¹ to A ¹⁶ represents a fluorine atom, but from the viewpoint of improving brightness by forming an association between two molecules of the phthalocyanine compound (1), at least one of A ¹ to A ⁴ represents a fluorine atom. wherein one or more of A ⁵ to A ⁸ are fluorine atoms, one or more of A ⁹ to A ¹² are fluorine atoms, and one or more of A ¹³ to A ¹⁶ are fluorine atoms Two or more of A ¹ to A ⁴ are fluorine atoms, two or more of A ⁵ to A ⁸ are fluorine atoms, and two or more of A ⁹ to A ¹² are fluorine atoms. is an atom, and two or more of A ¹³ to A ¹⁶ are fluorine atoms.

One or more of A ¹ to A ¹⁶ represent a group represented by the general formula (2), and from the viewpoint of solubility in solvents, one or more of A ¹ to A ⁴ may be A group represented by the formula (2), at least one of A ⁵ to A ⁸ being a group represented by the general formula (2), and at least one of A ⁹ to A ¹² being the general It is preferably a group represented by the formula (2), and at least one of A ¹³ to A ¹⁶ is a group represented by the general formula (2), and two of A ¹ to A ⁴ At least one of A 5 to A 8 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 of A ⁹ to A ¹² More preferably, at least one is a group represented by the general formula (2), and two or more of A ¹³ to A ¹⁶ are groups represented by the general formula (2).
In particular, from the viewpoint of color tone, brightness, and solubility in a solvent, which are required for color filters, A ² , A ³ , A ⁶ , A ⁷ , A ¹⁰ , A ¹¹ , A ¹⁴ , and A ¹⁵ are ), and A ¹ , A ⁴ , A ⁵ , A ⁸ , A ⁹ , A ¹² , A ¹³ , and A ¹⁶ are fluorine atoms.

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

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

(A) The coloring agent may contain other coloring agents in addition to the phthalocyanine compound (1). Other colorants include pigments and dyes. Among these, green pigments, green dyes, yellow pigments, yellow dyes, and the like are preferably used when used for green pixels.
As a green pigment, C.I. I. Pigment Green 7, 36, 58, 59, 62, 63, etc., and C.I. I. Pigment Green 58 is preferred.
Among green dyes classified as dyes in the Color Index, C.I. I. C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and C.I. I. As an acid dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Modant Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like. Among these, C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 are preferred.

As a 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 1:1 complexes of azobarbituric acid with nickel represented by the following formula (i) or tautomers thereof, other compounds is inserted (hereinafter sometimes referred to as "nickel azo complex represented by formula (i)").

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

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

Examples of yellow dyes include barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Specific examples thereof include specific compounds described in JP-A-2010-168531.
Among those classified as dyes in 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. 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 derivatives thereof 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 , 136, 138, 141 and the like. Furthermore, C.I. I. C.I. I. 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, 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, more preferably 0.04 μm or less. A method such as the solvent salt milling described above is preferably used for atomization of the pigment.

The content of (A) the colorant in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass in the total solid content of the colored resin composition 30% by mass or more is more preferable, 35% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is more preferable, and 45% by mass or less is Especially preferred. Color characteristics such as luminance and color gamut tend to be improved by making it equal to or higher than the lower limit, and pattern formability tends to be improved by making it equal to or lower than the upper limit.

The content of the phthalocyanine compound (1) in the colored resin composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 8% by mass or more, and 10% by mass in the total solid content of the colored resin composition. 15% by mass or more is more preferable, 20% by mass or more is particularly preferable, 45% by mass or less is preferable, 40% by mass or less is more preferable, 35% by mass or less is more preferable, and 30% by mass or less is More preferably, 25% by mass or less is particularly preferable. Color characteristics such as luminance and color gamut tend to be improved by making it equal to or higher than the lower limit, and pattern formability tends to be improved by making it equal to or lower than the upper limit.

When other colorants are included, the content is not particularly limited, but the total solid content of the colored resin composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further 3% by mass or more. It is preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less. Color characteristics such as luminance and color gamut tend to be improved by making it equal to or higher than the lower limit, and pattern formability tends to be improved by making it equal to or lower than the upper limit.

[1-2] (B) solvent (B) solvent dissolves or disperses the colorant, alkali-soluble resin, photopolymerization initiator, and other components in the colored resin composition or pigment dispersion of the present invention, has the function of adjusting
Any solvent (B) may be used as long as it can dissolve or disperse each component.

Examples of such solvents 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, propylene glycol mono-n-butyl ether, Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, 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;

glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl glycol alkyl 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, diamyl ether, ethyl isobutyl ether, dihexyl ether;
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, methyl nonyl ketone, methoxymethyl pentanone ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 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;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
ether ketones such as methoxymethylpentanone;
nitriles such as acetonitrile and benzonitrile;

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

When forming pixels of a color filter by photolithography, a solvent with a boiling point in the range of 100 to 200° C. (under a pressure of 1013.25 [hPa]; hereinafter, the same applies to all boiling points) is selected. is preferred. More preferably, it has a boiling point of 120-170°C.
Glycol alkyl ether acetates are preferred because they have a good balance of coatability, surface tension, etc. in the solvent and relatively high solubility of the constituent components in the composition.

Glycol alkyl ether acetates may be used alone, or may be used in combination with other solvents. Glycol monoalkyl ethers are particularly preferred as solvents to be used in combination. Among them, propylene glycol monomethyl ether is particularly preferable from the viewpoint of the solubility of the components in the composition. Glycol monoalkyl ethers have a high polarity, and if the amount added is too large, the pigment tends to aggregate, and the viscosity of the colored resin composition to be obtained later tends to decrease, resulting in a decrease in storage stability. 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. The combined use of such a high boiling point solvent makes the colored resin composition difficult to dry, but has the effect of making it difficult for the interrelationships of the pigment dispersion to be destroyed due to rapid drying. The content of the high-boiling solvent is preferably 3% to 50% by mass, more preferably 5% to 40% by mass, and particularly preferably 5% to 30% by mass, relative to the solvent (B). By making it equal to or higher than the above lower limit, for example, it tends to be easy to avoid causing foreign matter defects due to precipitation and solidification of coloring material components at the tip of the slit nozzle. It tends to be easy to avoid causing problems such as poor tact time in the vacuum drying process and pre-baking pin marks due to slow drying speed.
The solvent with a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, the solvent with a boiling point of 150°C or higher may not be included separately.
Examples of preferred high-boiling solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, and 1,6-hexanol diacetate. Acetate, triacetin and the like.

When forming pixels of a color filter by an inkjet method, a solvent having a boiling point of generally 130° C. or higher and 300° C. or lower, preferably 150° C. or higher and 280° C. or lower is suitable. When the content is at least the above lower limit, the uniformity of the resulting coating film tends to be improved, and when the content is at most the above upper limit, the amount of residual solvent during firing tends to be reduced.
From the viewpoint of the uniformity of the coating film to be obtained, the vapor pressure of the solvent is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less.

In the production of color filters using the inkjet method, the ink emitted from the nozzle is very fine, ranging from several pL to several tens of pL. - Tend to dry out. In order to avoid this, the solvent preferably has a higher boiling point, and specifically, it preferably contains a solvent having a boiling point of 180° C. or higher. More preferably, it contains a solvent with a boiling point of 200° C. or higher, particularly preferably 220° C. or higher. In addition, 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 making it more than the said lower limit, there exists a tendency for the evaporation prevention effect of the solvent from a droplet to be fully exhibited easily.

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

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

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

[1-3] (C) Alkali-Soluble Resin The colored resin composition of the present invention contains (C) an alkali-soluble resin. By containing (C) an alkali-soluble resin, it is possible to achieve both film curability by photopolymerization and solubility by a developer.
(C) Alkali-soluble resins include, for example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179 and the like can be used known polymer compounds described in each publication, etc., but among them, the following (C-1) to (C- 5) and the like.
(C-1): for a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, an unsaturated monobasic acid is added to at least part of the epoxy groups of the copolymer; A resin to be added, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction (hereinafter sometimes referred to as “resin (C-1)”). )
(C-2) Linear alkali-soluble resin containing a carboxyl group in the main chain (hereinafter sometimes referred to as "resin (C-2)")
(C-3) Resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter sometimes referred to as "resin (C-3)").
(C-4) (Meth) acrylic resin (hereinafter sometimes referred to as "resin (C-4)")
(C-5) Epoxy (meth)acrylate resin having a carboxyl group (hereinafter sometimes referred to as "resin (C-5)")
Of these, the resin (C-1) is particularly preferred, which will be described in detail below.

Incidentally, the resins (C-2) to (C-5) may be any as long as they are dissolved by an alkaline developer and have solubility to the extent that the intended development processing can be carried out. Those described as the same items in Japanese Patent Application Laid-Open No. 2009-025813 can be preferably employed.

(C-1) adding an unsaturated monobasic acid to at least part of the epoxy groups of a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer; or an alkali-soluble resin obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction. (Meth)acrylate 5 to 90 mol% and other radically polymerizable monomer 10 to 95 mol% of the copolymer, 10 to 100 mol% of the epoxy group of the copolymer is unsaturated A resin obtained by adding a basic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol % of the hydroxyl groups generated by the addition reaction.

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

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

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

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

Mono(meth)acrylates having a structure represented by formula (V) may be used singly or in combination of two or more.

As the mono (meth) acrylate having the structure represented by the general formula (V), various known ones can be used as long as it has the structure. ) acrylates are preferred.

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

In a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer, the content of repeating units derived from the mono(meth)acrylate represented by the general formula (VI) is It preferably contains 5 to 90 mol%, more preferably 10 to 70 mol%, and particularly preferably 15 to 50 mol% of repeating units derived from other radically polymerizable monomers. .

In addition, other than the mono(meth)acrylate represented by the general formula (VI), other radically polymerizable monomers are not particularly limited, but specific examples include styrene and styrene. vinyl aromatics such as α-, o-, m-, p-alkyl, nitro, cyano, amide and ester derivatives; dienes such as butadiene, 2,3-dimethylbutadiene, isoprene and chloroprene; (meth)acrylic acid methyl, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, ( tert-butyl meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylate Lauryl acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Propargyl (meth)acrylate, Phenyl (meth)acrylate, Naphthyl (meth)acrylate, Anthracenyl (meth)acrylate, Anthraninonyl (meth)acrylate, Piperonyl (meth)acrylate , (meth)salicyl acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate , Cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, (meth)acrylic perfluoro-iso-propyl acid, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxy (meth)acrylate (Meth)acrylic acid esters such as ethyl, (meth)acrylic acid-2-hydroxypropyl; (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N- Diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth) (a) (meth)acrylic acid amides such as acrylic acid N,N-di-iso-propylamide and (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride , vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl compounds such as vinyl acetate; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N-(4-hydroxyphenyl)maleimide; N-(meth)acryloylphthalimide and the like.

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

A well-known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth)acrylate and the other radically polymerizable monomer. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and commonly used organic solvents can be used.
Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate and butyl carbitol acetate; propylene glycol monoalkyl ether acetates; acetic acid esters such as dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol dialkyl Ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; hydrocarbons such as decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; lactate esters such as methyl lactate, ethyl lactate and butyl lactate; be done. These solvents may be used alone or in combination of two or more.

The amount of these solvents to be used is usually 30 to 1000 parts by mass, preferably 50 to 800 parts by mass, per 100 parts by mass of the resulting copolymer. By setting the amount of the solvent to be used within the above range, there is a tendency that the molecular weight of the copolymer can be easily controlled.
In addition, the radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and commonly used organic peroxide catalysts and azo compound catalysts can be used. can be done. Examples of organic peroxide catalysts include those classified into known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters and peroxydicarbonates.

Specific examples include benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-2-ethyl Hexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy)hexyl-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylperoxide, dicumylhydroperoxide, acetylperoxide, bis(4-t-butylcyclohexyl)peroxide Oxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxy) 3,3,5-trimethylcyclohexane , 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane and the like.

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

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

In the present invention, the copolymer of the epoxy group-containing (meth)acrylate and the other radically polymerizable monomer includes 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth)acrylate, and other 10 to 95 mol% of repeating units derived from a radically polymerizable monomer, preferably those consisting of 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and the former 30 to Especially preferred is one consisting of 70 mol % and 70 to 30 mol % of the latter.

By setting the content ratio of the repeating unit derived from the epoxy group-containing (meth)acrylate to the above lower limit or more, there is a tendency that the amount of the unsaturated monobasic acid or polybasic acid anhydride to be added becomes sufficient. By setting the content of repeating units derived from other radically polymerizable monomers to the lower limit or more, heat resistance and strength tend to be sufficient.
Subsequently, an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali soluble components).

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

By adding such a component, polymerizability can be imparted to the resin (C-1).
These unsaturated monobasic acids are usually added to 10 to 100 mol %, preferably 30 to 100 mol %, more preferably 50 to 100 mol % of the epoxy groups of the copolymer. By making it more than the said lower limit, there exists a tendency for the aging stability of a colored resin composition to become favorable. In addition, a well-known method can be employ|adopted as a method of adding an unsaturated monobasic acid to the epoxy group of a copolymer.

Further, known polybasic acid anhydrides to be added to hydroxyl groups produced when unsaturated monobasic acids are added to epoxy groups of the copolymer can be used.
Dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone Tribasic or higher acid anhydrides such as tetracarboxylic anhydride and biphenyltetracarboxylic anhydride can be mentioned. Among them, tetrahydrophthalic anhydride and/or succinic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the resin (C-1).
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy groups of the copolymer, preferably 20 to 90 mol. %, more preferably 30 to 80 mol %. When the content is equal to or less than the above upper limit, there is a tendency that the residual film ratio during development becomes favorable, and when the content is equal to or more than the above lower limit, there is a tendency that the solubility becomes sufficient. In addition, a well-known method can be employ|adopted as a method of adding a polybasic acid anhydride to the said hydroxyl group.

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

Alternatively, both of these may be added.
Specific examples of glycidyl ether compounds having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. Commercially available products include, for example, Nagase ChemteX Co., Ltd. trade names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", " Denacol EX-171”, “Denacol EX-192”, etc.

The structure of such a resin is already known, as described in, for example, JP-A-8-297366 and JP-A-2001-89533.
The polystyrene equivalent weight average molecular weight (Mw) measured by GPC of the resin (C-1) is not particularly limited, but is preferably from 3,000 to 100,000, and particularly preferably from 5,000 to 50,000. When the content is at least the above lower limit, heat resistance and film strength tend to be improved, and when the content is at most the above upper limit, solubility in a developing solution tends to be improved. As a measure of the molecular weight distribution, the weight average molecular weight (Mw)/number average molecular weight (Mn) ratio is preferably 2.0 to 5.0.

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

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

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

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

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned.
Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred from the viewpoint of patterning properties, and more preferred. is tetrahydrophthalic acid, biphenyltetracarboxylic acid.

(c1) The content of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, and 20 mol. % or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, particularly preferably 50 mol% or more, most preferably 65 mol% or more, and preferably 95 mol% or less, 90 mol % or less, more preferably 85 mol % or less, even more preferably 80 mol % or less, particularly preferably 75 mol % or less, most preferably 70 mol % or less. When the content is at least the above lower limit, the coating film curability tends to be improved during exposure to ultraviolet rays, and when the content is at most the above upper limit, the alkali solubility tends to be improved during alkali development.

(c1) The content of the partial structure represented by the general formula (I') contained in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 10 mol% or more, 20 mol% or more is more preferable, 30 mol% or more is still more preferable, 40 mol% or more is still more preferable, 50 mol% or more is particularly preferable, 65 mol% or more is most preferable, and 95 mol% or less is preferable, It is more preferably 90 mol % or less, still more preferably 85 mol % or less, even more preferably 80 mol % or less, particularly preferably 75 mol % or less, most preferably 70 mol % or less. When the content is at least the above lower limit, the coating film curability tends to be improved during exposure to ultraviolet rays, and when the content is at most the above upper limit, the alkali solubility tends to be improved during alkali development.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain contains the partial structure represented by the general formula (I), the other partial structure is not particularly limited. From the viewpoint of alkali solubility, it is also preferable to have, for example, a partial structure represented by the following general formula (II).

^In formula (II) above, R3 represents a hydrogen atom or a methyl group, and ^R4 represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or a substituent. represents an alkenyl group which may have

( ^R4 )
In formula (II) above, R ⁴ represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. .
Alkyl groups for R ⁴ include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, It is more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

Specific examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of developability, a dicyclopentanyl group or a dodecanyl group is preferred, and a dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The aromatic ring group for R ⁴ includes monovalent aromatic hydrocarbon ring groups and monovalent aromatic heterocyclic groups. The carbon number is preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene groups such as ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
Further, the aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. , imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furfuran ring, thienofuran ring, benzoisoxazole ring, benzoiso thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring groups such as Among these, from the viewpoint of developability, a benzene ring group or a naphthalene ring group is preferred, and a benzene ring group is more preferred.
Examples of substituents that the aromatic ring group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group and epoxy group. , an oligoethylene glycol group, a phenyl group, a carboxyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Alkenyl groups for R ⁴ include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

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

Examples of substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Thus, R ⁴ represents an optionally substituted alkyl group, an optionally substituted aromatic ring group, or an optionally substituted alkenyl group. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability and film strength.

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

(c1) When the acrylic copolymer resin contains a partial structure represented by the general formula (I), the other partial structure included is by improving the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin. From the standpoint of alkali solubility of the phthalocyanine compound (1), it is preferred that the partial structure represented by the following general formula (III) is included.

In formula (III) above, R ⁵ represents a hydrogen atom or a methyl group, R ⁶ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or a substituted represents an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group. t represents an integer of 0 to 5;

( ^R6 )
In the above formula (III), R ⁶ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, or a carboxyl group. , a halogen atom, an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
Alkyl groups for R ⁶ include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

Specific examples of alkyl groups include methyl, ethyl, cyclohexyl, dicyclopentanyl, and dodecanyl groups. Among these, from the viewpoint of heat resistance, a dicyclopentanyl group or a dodecanyl group is preferable, and a dicyclopentanyl group is more preferable.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Alkenyl groups for R ⁶ include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

Specific examples of alkenyl groups include a vinyl group, an allyl group, a 2-propen-2-yl group, a 2-buten-1-yl group, a 3-buten-1-yl group, a 2-penten-1-yl group, 3-penten-2-yl group, hexenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like. Among these, a vinyl group or an allyl group is preferred, and a vinyl group is more preferred, from the viewpoint of exposure sensitivity during ultraviolet exposure.

Examples of substituents that the alkenyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

Alkynyl groups for R ⁶ include linear, branched and cyclic alkynyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

Specific examples of alkynyl groups include 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl, 1, 4-pentadien-3-yl group, 1,3-pentadien-5-yl group, 1-hexyn-6-yl group, and the like.

Examples of substituents that the alkynyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The halogen atom for R ⁶ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of the storage stability of the acrylic copolymer resin.

Alkoxy groups for R ⁶ include linear, branched and cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

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

Examples of substituents that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkylsulfide group for R ⁶ includes linear, branched and cyclic alkylsulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less. By setting it to the above lower limit or more, the lipophilicity tends to be improved and the solubility in a solvent tends to be improved. be.

Specific examples of alkylsulfide groups include methylsulfide, ethylsulfide, propylsulfide, and butylsulfide groups. Among these, a methylsulfide group or an ethylsulfide group is preferable from the viewpoint of developability.

Substituents that the alkyl group in the alkylsulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferred.

Thus, R ⁶ is an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen represents an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkylsulfide group. preferable.

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

(c1) The content of the partial structure represented by the general formula (III) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 1 mol% or more, and 2 mol% or more. is more preferably 5 mol% or more, particularly preferably 8 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, and 20 mol% or less Especially preferred. When the content is at least the lower limit, the affinity between the phthalocyanine compound (1) and the acrylic copolymer resin tends to improve, and the alkali solubility tends to be improved. As the ratio increases, the alkali solubility tends to improve.

(c1) When the acrylic copolymer resin having an ethylenically unsaturated group in the side chain has a partial structure represented by the general formula (I), the other partial structure may be the following general formula from the viewpoint of developability: It is also preferred to have a partial structure represented by (IV).

In formula (IV) above, ^R7 represents a hydrogen atom or a methyl group.

(c1) The content of the partial structure represented by the general formula (IV) in the acrylic copolymer resin having an ethylenically unsaturated group in the side chain is not particularly limited, but is preferably 5 mol% or more, It is more preferably 10 mol % or more, more preferably 20 mol % or more, more preferably 80 mol % or less, more preferably 70 mol % or less, and even more preferably 60 mol % or less. Alkali solubility tends to improve by setting it to the above lower limit or more, and the storage stability of the colored resin composition tends to improve by setting it to the above upper limit or less.

On the other hand, the acid value of (C) the alkali-soluble resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g or more. 60 mgKOH/g or more is particularly preferable, 300 mgKOH/g or less is preferable, 250 mgKOH/g or less is more preferable, 200 mgKOH/g or less is still more preferable, and 150 mgKOH/g or less is even more preferable. Alkali solubility tends to improve by setting it to the above lower limit or more, and the storage stability of the colored resin composition tends to improve by setting it to the above upper limit or less.

(C) The weight average molecular weight (Mw) of the alkali-soluble resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, even more preferably 7000 or more, and particularly preferably It is 8,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less. When the content is at least the above lower limit, heat resistance and coating film curability tend to improve, and when the content is at most the above upper limit, alkali solubility tends to improve.

Although the content of (C) the alkali-soluble resin in the colored resin composition of the present invention is not particularly limited, the total solid content of the colored resin composition is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, particularly preferably 30% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably It is 50% by mass or less, more preferably 40% by mass or less. By setting the thickness to the above lower limit or more, a firm film can be obtained, and there is a tendency that the adhesion to the substrate is excellent. In addition, by making it equal to or less than the above upper limit, there is a tendency that the penetration of the developing solution into the exposed portion is low, and deterioration of the surface smoothness and sensitivity of the pixel can be suppressed.

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

The (D) photopolymerization initiator in the colored resin composition of the present invention contains a photopolymerization initiator (d1) having a fluorene skeleton (hereinafter sometimes referred to as "photopolymerization initiator (d1)").
By including the photopolymerization initiator (d1), the π-π interaction between the fluorene skeleton and the phthalocyanine ring of the phthalocyanine compound (1) suppresses aggregate formation of the phthalocyanine compound (1), resulting in light scattering. is less likely to occur, and the decrease in contrast can be suppressed.

Among the photopolymerization initiators (d1) having a fluorene skeleton, photopolymerization initiators represented by the following general formula (I) are preferred from the viewpoint of solubility in solvents and inhibition of contrast deterioration.

In formula (I), R ^d1 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ^d2 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
p represents 0 or 1;
R ^d3 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3;
R ^d4 and R ^d5 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group. R ^d4 and R ^d5 may combine with each other to form a ring.

(R ^d1 )
In formula (I) above, R ^d1 represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
The alkyl group for R ^d1 may be linear, branched, cyclic, or a combination thereof. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 10 or less, more preferably 7 or less, still more preferably 5 or less, particularly preferably 3 or less, most preferably 2 or less, and usually 1 or more. By setting the number of carbon atoms in the alkyl group to the above upper limit or less, the solubility in solvents is improved, and the π-π interaction with the phthalocyanine ring suppresses the formation of aggregates of the phthalocyanine compound (1), resulting in contrast. It tends to suppress the decline.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl and cyclohexyl groups. Among these, from the viewpoint of sensitivity, a methyl group, an ethyl group, a propyl group, or a butyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.
Examples of substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I and a hydroxyl group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferred. From the viewpoint of sensitivity, it is preferably unsubstituted.

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

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be monocyclic or condensed. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have one free valence, Groups such as acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring and carbazole ring having one free valence. ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Groups such as pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable.

Among these, from the viewpoint of sensitivity, R ^d1 is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and further preferably a methyl group or an ethyl group. A methyl group is particularly preferred.

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

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

Examples of substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms. A carbonyl group, a halogen atom such as F, Cl, Br, and I, a hydroxyl group, and the like, and an alkoxy group having 1 to 3 carbon atoms is preferable from the viewpoint of solvent solubility. From the viewpoint of sensitivity, it is preferably unsubstituted.

Specific examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group and the like. Among these, from the viewpoint of solvent solubility, isopentyl group, cyclohexylmethyl group, cyclopentylethyl group, or cyclohexylethyl group is preferable, cyclopentylethyl group or cyclohexylethyl group is more preferable, and cyclohexylethyl group is still more preferable.

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

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be monocyclic or condensed. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have one free valence, Groups such as acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring and carbazole ring having one free valence. ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Groups such as pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring.
Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group is preferred. The alkyl chain portion of the substituent may be linear or branched, and further has a substituent such as an alkoxy group having 1 to 3 carbon atoms, an alkylthio group having 1 to 3 carbon atoms, a halogen atom, a hydroxyl group, a nitro group, or the like. You may have

Among these, R ^d2 is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and a methyl group, from the viewpoint of solubility in solvents and suppression of contrast deterioration. , ethyl group and propyl group are more preferred, and methyl group is particularly preferred.

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

(R ^d3 )
In formula (I) above, R ^d3 represents an arbitrary monovalent substituent.
Optional monovalent substituents include alkyl groups having 1 to 10 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 10 carbon atoms such as methoxy group and ethoxy group; F, Cl, Br, I and the like. a halogen atom; an acyl group having 1 to 10 carbon atoms; an alkyl ester group having 1 to 10 carbon atoms; an alkoxycarbonyl group having 1 to 10 carbon atoms; a halogenated alkyl group having 1 to 10 carbon atoms; Aromatic ring group; amino group; aminoalkyl group having 1 to 10 carbon atoms; hydroxyl group; nitro group; CN group; optionally substituted benzoyl group; optionally substituted thenoyl group, etc. are mentioned. Examples of substituents that the benzoyl group or thenoyl group may have include an alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. may Among these, a nitro group is preferable from the viewpoint of suppression of contrast deterioration.
In R ^d3 , when q is 2 or more, a plurality of R ^d3 may combine to form a ring. The ring may be an aliphatic ring or an aromatic ring.

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

(R ^d4 and R ^d5 )
In formula (I), R ^d4 and R ^d5 each independently represent a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aromatic ring group.

The alkyl group for R ^d4 and R ^d5 may be linear, branched, cyclic, or a combination thereof. is more preferred.
Although the number of carbon atoms in the alkyl group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, particularly preferably 5 or more, and preferably 10 or less, more preferably 8 or less. , more preferably 6 or less, particularly preferably 4 or less. When the number of carbon atoms in the alkyl group is at least the lower limit, solvent solubility tends to be improved, and when the number of carbon atoms is at most the upper limit, sensitivity tends to be high.
Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl, and 2-ethylhexyl groups. etc. Among these, from the viewpoint of the balance between sensitivity and solvent solubility, an ethyl group, a propyl group, an isopropyl group, or a butyl group is preferred, an ethyl group or a propyl group is more preferred, and an ethyl group is even more preferred.
Examples of substituents that the alkyl group may have include an aromatic ring group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I and a hydroxyl group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms is preferred. From the viewpoint of sensitivity, it is preferably unsubstituted.

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

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be monocyclic or condensed. The aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, which have one free valence, Groups such as acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Moreover, the aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring and carbazole ring having one free valence. ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Groups such as pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring. Among these, from the viewpoint of solvent solubility, a benzene ring or a naphthalene ring having one free valence is preferred, and a benzene ring having one free valence is more preferred.

Examples of substituents that the aromatic ring group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, F, Cl, Br, I , a hydroxyl group, a nitro group, etc., and from the viewpoint of solvent solubility, an alkoxy group having 1 to 3 carbon atoms or a hydroxyl group is preferable. From the viewpoint of sensitivity, it is preferably unsubstituted.

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

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

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

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

(D) The photoinitiator may further contain another photoinitiator (d2) in addition to the photoinitiator (d1).
Other photopolymerization initiators (d2) include, for example, titanocene derivatives including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197; hexaarylbiimidazole derivatives described; halomethylated oxadiazole derivatives described in JP-A-10-39503, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl- Radical activators such as α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime esters described in JP 2000-80068, JP 2006-36750, etc. derivatives and the like.

Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluoro phenyl-1-yl), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl- 1-yl), dicyclopentadienyl titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopenta dienyl) titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl), dicyclo pentadienyl titanium [2,6-di-fluoro-3-(pyro-1-yl)-phenyl-1-yl] and the like.

Further, biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole. dimer, 2-(2′-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2′-methoxyphenyl)-4,5-diphenylimidazole dimer, (4′-methoxy phenyl)-4,5-diphenylimidazole dimer and the like.

Further, halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2′-(6″-benzofuryl)vinyl)]-1,3,4-oxadiazole, 2 -trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

Further, halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

Further, α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo eth, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-( 4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone and the like.

As oxime ester derivatives, JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, JP-A-2012- Examples thereof include oxime ester compounds described in Japanese Patent Application Laid-Open No. 519191 and the like. Among them, from the viewpoint of sensitivity, methyl 4-acetoxyimino-5-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-5-oxopentanoate, and as a product name, OXE- 01, OXE-02, OXE-03 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG314 (manufactured by Changzhou Tenryu), NCI-831, NCI-930 (manufactured by ADEKA), etc. can be cited as preferable.
The other photopolymerization initiators (d2) may be used alone or in combination of two or more.

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

In addition to (D) the photopolymerization initiator, a chain transfer agent may be used. A chain transfer agent is a compound that has the function of receiving a generated radical and transferring the radical to another compound.
As the chain transfer agent, various compounds can be used as long as they are compounds having the above functions. It is more preferable to use a compound having a mercapto group. This is probably because bond cleavage is likely to occur due to the small SH bond energy, and hydrogen abstraction reaction and chain transfer reaction are likely to occur. Effective in improving sensitivity and surface curability.

Mercapto group-containing compounds include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 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, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol Bis(3-mercaptopropionate), ethylene glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyl tristhiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3- mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine Examples include aliphatic mercapto group-containing compounds such as -2,4,6(1H,3H,5H)-trione, and compounds having a plurality of mercapto groups are particularly preferred from the viewpoint of surface smoothness.

Among these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred among the mercapto group-containing compounds having an aromatic ring, and among the aliphatic mercapto group-containing compounds, trimethylolpropane tris (3- mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate) rate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H) - Trione is preferred.

In terms of sensitivity, aliphatic mercapto group-containing compounds are preferred, and specifically, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol. tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5- Tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) is more preferred.
These various things can be used individually by 1 type, or in mixture of 2 or more types.

In the colored resin composition of the present invention, the content of (D) the photopolymerization initiator is not particularly limited, preferably 1% by mass or more in the total solid content of the colored resin composition, more preferably 3% by mass or more, 5% by mass or more is more preferable, 7% by mass or more is particularly preferable, 20% by mass or less is preferable, 15% by mass or less is more preferable, 12% by mass or less is more preferable, and 10% by mass or less is particularly preferable. When the amount is at least the lower limit, the patterning properties after development tend to be ensured, and when the amount is at most the upper limit, a decrease in transmittance due to excessive addition of the photopolymerization initiator tends to be suppressed.

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

[1-5] Other solid content The colored resin composition of the present invention can further contain solid content other than the above components, if necessary. Such components include photopolymerizable monomers, dispersants, dispersing aids, surfactants, and the like.

[1-5-1] Photopolymerizable monomer The photopolymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular-weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as a photopolymerizable monomer) (referred to as "ethylenic compounds") are preferred. 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 actinic rays, it undergoes addition polymerization and cures due to the action of a photopolymerization initiator. In addition, the monomer in the present invention means a concept corresponding to a so-called polymer substance, and means a concept including dimers, trimers, and oligomers in addition to monomers in a narrow sense.
In the present invention, it is particularly desirable to use polyfunctional ethylenic monomers having two or more ethylenic double bonds in one molecule. The number of ethylenic double bonds possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. When the concentration is equal to or higher than the lower limit, there is a tendency to increase the sensitivity, and when the concentration is equal to or lower than the upper limit, the solubility in a solvent tends to be improved.

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

Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid moiety of these acrylates may be replaced with a methacrylic acid ester, an itaconic acid ester with an itaconic acid moiety, a crotonic acid ester with a crotonic acid moiety, or a maleic acid moiety with a maleic acid moiety. Ester etc. are mentioned.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like.
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, and may be a mixture. Representative examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. and condensates of glycerin.

Examples of ethylenic compounds 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 diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy(1,1,1-triacryloyloxymethyl)propane, Examples include reaction products with (meth)acryloyl group-containing hydroxy compounds 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 divinyl phthalate are also useful.
Also, 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 the unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. Preference is given to polyfunctional monomers, particularly preferred are those in which the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol in the ester.

One of these monomers may be used alone, but since it is difficult to use a single compound in terms of production, two or more of them may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as a monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH/g, particularly preferably 5 to 30 mgKOH/g. When it is at least the above lower limit, there is a tendency that development dissolution characteristics can be improved, and when it is at most the above upper limit, production and handling are improved, and photopolymerization performance, surface smoothness of pixels, etc. are improved. Curability tends to be improved. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when polyfunctional monomers having no acid groups are used in combination, the acid groups of the entire polyfunctional monomer should be adjusted to fall within the above range. is preferred.

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

In the present invention, from the viewpoint of improving the chemical resistance of pixels and the linearity of the edges of pixels, it is preferable to use the polymerizable monomers described in JP-A-2013-195971. From the viewpoint of achieving both sensitivity of the coating film and shortening of development time, it is preferable to use the polymerizable monomer described in JP-A-2013-195974.

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

[1-5-2] Dispersant, Dispersing Aid When the colored resin composition of the present invention contains a pigment as (A) the colorant, it preferably contains a dispersant for the purpose of stably dispersing the pigment. Among the dispersants, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time.
Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyesters. Mention may be made of system dispersants. Specific examples of these dispersants include trade names of EFKA (registered trademark, manufactured by BASF), DisperBYK (registered trademark, manufactured by BYK-Chemie), Disparon (registered trademark, manufactured by Kusumoto Kasei), SOLSPERSE (registered trademark, manufactured by Lubri Zol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), and those described in JP-A-2013-119568.

Among polymeric dispersants, block copolymers having functional groups containing nitrogen atoms are preferred, and acrylic block copolymers are more preferred, from the viewpoint of dispersibility and storage stability.
A block copolymer having a functional group containing a nitrogen atom includes an A block having a quaternary ammonium base and/or an amino group in a side chain and a B block having no quaternary ammonium base and/or an amino group. AB block copolymers and/or BAB block copolymers are preferred.

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

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituted and R ¹ and R ² may combine to form a cyclic structure. ^R3 is a hydrogen atom or a methyl group. X is a divalent linking group.

In the above formula (1), the number of carbon atoms in the optionally substituted alkyl group is not particularly limited, but is usually 1 or more, preferably 10 or less, more preferably 6 or less. It is preferably 4 or less, more preferably 4 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

In the above formula (1), the number of carbon atoms in the optionally substituted aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less. Preferably, it is 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 and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the optionally substituted aralkyl group in the above formula (1) is not particularly limited, but is usually 7 or more, preferably 16 or less, more preferably 12 or less. Preferably, it is 9 or less. Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, a phenylisopropyl group and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of dispersibility, storage stability, electrical reliability, and developability, it is preferable that each of R ¹ and R ² is independently an optionally substituted alkyl group, a methyl group, or More preferably, it is 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 are unnecessary from the viewpoint of ease of synthesis. Substitution is preferred.

In the above formula (1), the cyclic structure formed by combining R ¹ and R ² may be, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of these. are mentioned. The nitrogen-containing heterocyclic ring is preferably non-aromatic, more preferably saturated. Specifically, for example, the following (IV) is exemplified.

These cyclic structures may further have a substituent.

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, a -CONH-R ¹³ - group, a -COOR ¹⁴ - group [ provided that 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], preferably -COO-R ¹⁴ - group.

Further, the content 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, even more preferably 15 mol% or more, particularly preferably 20% or more, most preferably 25 mol% or more, and 90 mol% or less. is preferably 70 mol % or less, more preferably 50 mol % or less, and particularly preferably 40 mol % or less. Within the above range, there is a tendency that both dispersion stability and high brightness can be achieved.

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

In formula (2) above, R ¹⁰ is an ethylene group or a propylene group, R ¹¹ is an optionally substituted alkyl group, and R ¹² is a hydrogen atom or a methyl group.
n is an integer from 1 to 20;

Although the number of carbon atoms in the optionally substituted alkyl group in R ¹¹ in the above formula (2) is not particularly limited, it is usually 1 or more, preferably 2 or more, and 10 or less. is preferred, 6 or less is more preferred, and 4 or less is even more preferred. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included. Substituents which may be present include a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group, etc. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

In addition, 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 respect to a binder component such as a solvent. , 5 or less.

Further, the content of the repeating unit represented by the formula (2) in the total 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, preferably 30 mol % or less, more preferably 20 mol % or less, and even 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.

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

In formula (3) above, R ⁸ is an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. ^R9 is a hydrogen atom or a methyl group.

Although the number of carbon atoms in the optionally substituted alkyl group in R ⁸ of the above formula (3) is not particularly limited, it is usually 1 or more, preferably 1 or more, and 10 or less. is preferred, and 6 or less is more preferred. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and the like. is preferably a group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Also, it may be linear or branched. Moreover, a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group may be included.

The number of carbon atoms in the optionally substituted aryl group in R ⁸ of the formula (3) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 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 and an anthracenyl group. , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the optionally substituted aralkyl group in R ⁸ of the formula (3) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 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 phenylisopropyl group and the like. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or A phenylbutylene group is preferable, and a phenylmethylene group or a phenylethylene group is more preferable.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ⁸ is preferably an alkyl group or an aralkyl group, more preferably a methyl group, an ethyl group or a phenylmethylene group.
A halogen atom, an alkoxy group, etc. are mentioned as the substituent which the alkyl group in R< ⁸ > may have. Further, examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group, and the like. The chain alkyl group represented by R ⁸ includes both linear and branched alkyl groups.

Further, the content of the repeating unit represented by the formula (3) in the total 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 more preferably 70 mol % or less. Within the above range, there is a tendency that both dispersion stability and high brightness can be achieved.

The block copolymer contains repeating units 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). may have. Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- (Meth)acrylamide-based monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate glycidyl ether;

From the viewpoint of further increasing dispersibility, 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). Block copolymers are preferred. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Moreover, 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. Examples of such repeating units include the above-mentioned (meth)acrylic acid ester Examples thereof 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%. 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, styrene-based monomers such as α-methylstyrene; (meth) acrylic acid salt-based monomers such as (meth) acrylic acid chloride; (meth) acrylamides such as (meth) acrylamide and N-methylolacrylamide Examples include repeating units derived from monomers such as vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate; N-methacryloylmorpholine. The content of the repeating unit other than the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (3) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol %, but most preferably no such repeating units are contained in the B block.

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

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

Further, the molecular weight of the block copolymer is preferably in the range of 1000 to 30,000 in terms of polystyrene equivalent weight average molecular weight (hereinafter sometimes referred to as "Mw"). When it is within the above range, the dispersion stability is improved, and there is a tendency that dried foreign substances are less likely to occur during application by a slit nozzle method.

The block copolymer can be produced by a known method. For example, it can be produced by living polymerization of monomers into which the repeating units are introduced. As the living polymerization method, JP-A-9-62002, JP-A-2002-31713 and P.O. Lutz, P.; Masson et al, Polym. Bull. 12, 79 (1984), B.P. C. Anderson, G.; D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K.; Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Kouichi Ugi, Kouichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Kobunshi Ronbunshu, 46, 189 (1989), M. Kuroki, T.; Aida, J.; Am. Chem. Soc, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D. Y. Sogoh, W.; R. A known method described in Hertler et al, Macromolecules, 20, 1473 (1987) or the like can be employed.

When the colored resin composition of the present invention contains a pigment and a dispersant, the content of the dispersant is not particularly limited, but is preferably 0.5 parts by mass or more, more preferably 100 parts by mass of the pigment. is 5 parts by mass or more, more preferably 10 parts by mass or more, even 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, More preferably 40 parts by mass or less, particularly preferably 30 parts by mass or less. By setting it within the above range, there is a tendency that a coloring resin composition having excellent dispersion stability and high brightness can be obtained.

When the colored resin composition of the present invention contains a pigment, it may contain a pigment derivative or the like as a dispersing aid for improving the dispersibility of the pigment and improving the dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole-based and dioxazine-based pigments are included. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc., directly on the pigment skeleton, or on alkyl groups, aryl groups, complex groups, and the like. Those bonded via a ring group or the like can be mentioned, preferably a sulfonamide group, a quaternary salt thereof, and a sulfonic acid group, more preferably a sulfonic acid group. A single pigment skeleton may be substituted with a plurality of these substituents, or a mixture of compounds having different numbers of substitutions may be used. Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, Examples include sulfonic acid derivatives of diketopyrrolopyrrole pigments, sulfonic acid derivatives of dioxazine pigments, and the like.

[1-5-3] Surfactant As the surfactant, various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used, but the properties may be adversely affected. It is preferable to use a nonionic surfactant because it has a low The content of the surfactant is not particularly limited, but usually 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more in the total solid content of the colored resin composition, and further It is preferably used in an amount of 0.1% by mass or more, and usually 10% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.3% by mass or less.

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

When a colorant containing a pigment is prepared, first, predetermined amounts of a pigment, a solvent and a dispersant are weighed, and the colorant containing the pigment is dispersed in a dispersion treatment step to prepare a pigment dispersion. A paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used in this dispersion treatment step. Since the colorant is finely divided by performing this dispersing treatment, the coating property of the colored resin composition is improved, and the transmittance of the pixels in the color filter substrate of the product is improved.

When dispersing the pigment, as described above, it is preferable to use a dispersing aid or a dispersing resin as appropriate.
When performing dispersion treatment using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersing 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 appropriate dispersion time may vary depending on the composition of the pigment dispersion, the size of the sand grinder, and the like, and may be adjusted as appropriate.

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

When a pigment is not contained as a coloring agent, a uniform solution can be obtained by mixing a coloring agent, a solvent, an alkali-soluble resin, a photopolymerization initiator, and, if necessary, components other than those mentioned above. 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.
A color filter according to the present invention has pixels formed using the colored resin composition described above.

[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 materials include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly(meth)acryl. A thermosetting resin sheet such as a base resin, or various types of glass may be used. Among these, glass or heat-resistant resin is preferable from the viewpoint of heat resistance.

For the transparent substrate and the black matrix forming substrate, in order to improve surface physical properties such as adhesiveness, if necessary, corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. may be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. When thin films of various resins are formed, 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 A color filter according to the present invention can be manufactured by providing a black matrix on the transparent substrate described above, and usually forming red, green, and blue pixel images. Among red, green, and blue pixels, the colored resin composition is preferably used as a coating liquid for forming green pixels (resist pattern) (hereinafter sometimes abbreviated as “green resist”). Using the green resist, it is coated on a resin black matrix formation surface formed on a transparent substrate, or on a metal black matrix formation surface formed using a chromium compound or other light-shielding metal material, applying, heat drying, image exposure, Development and thermal curing processes are performed to form a pixel image.

A black matrix is formed on a transparent substrate using a light-shielding metal thin film or a colored resin composition for a black matrix. As the light-shielding metal material, chromium compounds such as chromium metal, chromium oxide, and chromium nitride, alloys of nickel and tungsten, and the like are used.
These metal light-shielding films are generally formed by a sputtering method. After forming a desired film pattern with a positive photoresist, chromium is treated with ceric ammonium nitrate and perchloric acid and/or nitric acid. and other materials are etched using an etchant suitable for the material, and finally the positive photoresist is removed with a special remover to form a black matrix. be able to.

In this case, first, a thin film of these metals or metal/metal oxides is formed on a transparent substrate by vapor deposition, sputtering, or the like. Next, after forming a coating film of a 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 black matrix is used, a black matrix is formed using a colored resin composition containing a black colorant. For example, black colorants such as carbon black, graphite, iron black, aniline black, cyanine black, and titanium black, or a plurality of black colorants, or inorganic or organic pigments, dyes, red, green, blue, etc. A black matrix can be formed using a colored resin composition containing a mixed black colorant in the same manner as in the method for forming pixel images of red, green and blue below.

[3-3] Formation of pixels On a transparent substrate provided with a black matrix, a colored resin composition of one of red, green, and blue is applied, dried, and then a photomask is overlaid on the coating film. A pixel image is formed by imagewise exposure through a photomask, development, and thermal curing or photocuring as necessary. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

Application of the colored resin composition for color filters can be carried out 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 greatly reduced, and there is no effect of mist that adheres when using the spin coating method, and the generation of foreign matter is suppressed. from the point of view.

If the thickness of the coating film is too large, it may become difficult to develop the pattern and it may become difficult to adjust the gap in the process of forming a liquid crystal cell. Color development may not be possible. 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 Drying of the coating film after applying the colored resin composition to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is dried by heating again. Pre-drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of solvent component and the performance of the dryer used. C. or lower, preferably 70.degree.

The temperature conditions for reheating and drying are preferably higher than the pre-drying temperature. °C or less. The drying time depends on the heating temperature, but is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes or less. The higher the drying temperature, the better the adhesiveness to the transparent substrate. As the drying step of the coating film, a reduced pressure drying method may be used in which the drying is performed in a reduced pressure chamber without raising the temperature.

[3-5] Exposure Step Imagewise exposure is carried out by overlaying a negative matrix pattern on the coating film of the colored resin composition and irradiating it with an ultraviolet or visible light source through this mask pattern. In this case, if necessary, exposure may be performed after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent deterioration of the sensitivity of the photopolymerizable layer due to oxygen. The light source used for the above image exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps, argon ion lasers, YAG lasers, Examples include laser light sources such as excimer lasers, nitrogen lasers, helium-cadmium lasers, and semiconductor lasers. An optical filter can also be used when irradiating and using the light of a specific wavelength.

[3-6] Development step The color filter according to the present invention is formed by subjecting the coating film using the colored resin composition according to the present invention to imagewise exposure with the light source described above, and then adding a surfactant and an alkaline compound. An image can be formed on the substrate by developing with an aqueous solution containing the substrate. This aqueous solution may further contain organic solvents, buffers, complexing agents, dyes or pigments.

Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate. , sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, inorganic alkaline compounds such as 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 compound. These alkaline compounds may be a mixture of two or more.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; Anionic surfactants such as salts, alkylnaphthalenesulfonates, alkylsulfates, alkylsulfonates, and sulfosuccinate ester salts, and amphoteric surfactants such as alkylbetaines and amino acids.

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

[3-7] Heat Curing Treatment The color filter after development is subjected to heat curing treatment. At this time, the heat curing treatment conditions are such that the temperature is usually 100° C. or higher, preferably 150° C. or higher, and usually 280° C. or lower, preferably 250° C. or lower, and the time is 5 minutes or more and 60 minutes or less. selected in the range. Through a series of these steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. The order of patterning the four colors is not limited to the order described above.

[3-8] Formation of transparent electrode The color filter according to the present invention can be used as a part of parts such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image in this state. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide may be provided on the image, if necessary. In addition, in some applications such as planar alignment driving system (IPS mode), the 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 aforementioned color filter. Hereinafter, a liquid crystal display device and an organic EL display device will be described in detail as image display devices.

[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 is usually formed by forming an alignment film on the color filter according to the present invention, dispersing spacers on the alignment film, and then bonding it to a counter substrate to form a liquid crystal cell. Liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete the process. The alignment film is preferably a resin film such as polyimide. A gravure printing method and/or a flexographic printing method is usually employed for forming the alignment film, and the thickness of the alignment film is set to several tens of nanometers. After hardening the alignment film by heat baking, the surface is treated by irradiation with ultraviolet rays or treatment with a rubbing cloth, so that the surface state is processed so that the tilt of the liquid crystal can be adjusted.

The spacer used has a size corresponding to the gap (clearance) with the counter substrate, and normally 2 to 8 μm is suitable. A photo-spacer (PS) made of a transparent resin film can be formed on the color filter substrate by photolithography and used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.

Although the gap between the opposing substrate and the bonding substrate varies depending on the application of the liquid crystal display device, it is usually selected in the range of 2 μm or more and 8 μm or less. After bonding to the opposing substrate, the portion other than the liquid crystal injection port is sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and/or heating to seal the periphery of the liquid crystal cell.
After the liquid crystal cell with its periphery sealed is cut into panels, the pressure is reduced in a vacuum chamber, the liquid crystal inlet is immersed in the liquid crystal, and then the chamber is leaked to inject the liquid crystal into the liquid crystal cell. . The degree of pressure reduction in the liquid crystal cell is usually 1×10 ⁻² Pa or more, preferably 1×10 ⁻³ or more, and usually 1×10 ⁻⁷ Pa or less, preferably 1×10 ⁻⁶ Pa or less. . Moreover, it is preferable to heat the liquid crystal cell when the pressure is reduced.

Heating and holding at reduced pressure is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in liquid crystal. 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 curing resin.
There is no particular limitation on the type of liquid crystal, and any known liquid crystal such as aromatic, aliphatic, polycyclic compounds, lyotropic liquid crystal, thermotropic liquid crystal, or the like may be used. Thermotropic liquid crystals include nematic liquid crystals, smestic liquid crystals, cholesteric liquid crystals, and the like, and any of them may be used.

[4-2] Organic EL display device When producing an organic EL display device having the color filter of the present invention, for example, as shown in FIG. A multicolor organic EL device is manufactured by laminating the organic light emitter 500 on the blue color filter formed with the organic protective layer 30 and the inorganic oxide film 40 interposed therebetween.

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

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

<Phthalocyanine compound A>
A phthalocyanine compound A having the following chemical structure synthesized according to Example 30 of JP-A-05-345861 was used.

<Phthalocyanine compound B>
5.00 g (18.8 mmol) of tetrachlorophthalonitrile, 3.32 g (18.8 mmol) of 2-cyclohexyl-5-methylphenol, 3.89 g (28.2 mmol) of potassium carbonate and 50 mL of acetonitrile were mixed and heated to 70°C. Heated and left to stir for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, filtered and concentrated. The resulting residue was recrystallized with acetonitrile to give 4.70 g of a mixture of intermediate A and intermediate B (yield 59%, purity 77.9%, intermediate A/intermediate B=73/23). Obtained. In addition, this purity is the value of the area% calculated from the result of the high performance liquid chromatography analysis.

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

3.00 g (7.15 mmol) of a mixture of Intermediate A and Intermediate B, 0.69 g (2.14 mmol) of zinc iodide and 7.2 g of benzonitrile were mixed and reacted at 170° C. for 6.5 hours. After completion of the reaction, the reaction solution was cooled and poured into 20 mL of methanol. After filtering the produced|generated solid content, it wash|cleaned with methanol and water, and obtained 2.62g (yield 84%) of the phthalocyanine compound B by drying under reduced pressure at 50 degreeC.

1 mg of phthalocyanine compound B was dissolved in 100 mL of DMSO (dimethyl sulfoxide), and the visible absorption spectrum was measured with a UV-visible spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation) using a 1 cm square quartz cell. The wavelength was 651.0 nm and the molar extinction coefficient (ε) was 4.08×10 ⁵ .

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

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

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

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

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

<Alkali-soluble resin B>
148.0 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution and heated 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 having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120°C for 2 hours. kept doing. Next, the inside of the reaction vessel was changed to air exchange, 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. After that, 39.0 parts by mass of succinic anhydride and 0.7 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin B thus obtained was 8000, and the acid value was 88 mgKOH/g.

<Alkali-soluble resin C>
145 parts by mass of propylene glycol monomethyl ether acetate was stirred under nitrogen substitution and heated to 120°C. 10 parts by mass of styrene, 90 parts by mass of glycidyl methacrylate, and 10 parts by mass of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120° C. for 2 hours. Next, the inside of the reaction vessel was changed to air exchange, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 50 parts by mass of acrylic acid, and the reaction was continued at 120°C for 6 hours. After that, 13 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 120° C. for 3.5 hours. The polystyrene equivalent weight average molecular weight Mw measured by GPC of the alkali-soluble resin C thus obtained was 9000, and the acid value was 25 mgKOH/g.

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

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

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

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

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

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

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

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

<Surfactant A>
Megafac F-559 (manufactured by DIC)

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

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

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

As is clear from Table 2, when the colored resin composition containing the phthalocyanine compound (1) as the green colorant was used as in Example 1, the brightness was high, while Comparative Examples 2 and 3 Chlorine atom-substituted phthalocyanine compounds B and C.I. I. When the colored resin composition containing Pigment Green 58 was used, the brightness was low.
In the phthalocyanine compound (1), the molecules easily associate with each other due to the π-π interaction between the phthalocyanine rings and the π-π interaction between the general formula (2). It is considered that the packing between molecules becomes denser, and the brightness is increased due to the formation of aggregates between two molecules.

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

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

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

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

Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the invention.

REFERENCE SIGNS LIST 10 transparent support substrate 20 pixel 30 organic protective layer 40 inorganic oxide film 50 transparent anode 51 hole injection layer 52 hole transport layer 53 light emitting layer 54 electron injection layer 55 cathode 100 organic EL element 500 organic light emitter

Claims (4)

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

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

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

(In formula (I), R ^d1 is an optionally substituted alkyl group or an optionally substituted
represents an aromatic ring group.
R ^d2 is an optionally substituted alkyl group or an optionally substituted aromatic ring group
represents
p represents 0 or 1;
R ^d3 represents an arbitrary monovalent substituent. q represents an integer of 0 to 3;
R ^d4 and R ^d5 are each independently an optionally substituted alkyl group having 4 or more carbon atoms
represents ) The colored resin composition according to claim 1, wherein the content of the phthalocyanine compound having the chemical structure represented by the general formula (1) is 5% by mass or more in the total solid content. A color filter having pixels formed using the colored resin composition according to claim 1 or 2 . An image display device comprising the color filter according to claim 3 .

Images