CN114253074A - Colored curable resin composition, color filter, and display device - Google Patents

Abstract

The invention aims to provide a colored curable resin composition and the like capable of providing a color filter with excellent deep color effect. The colored curable resin composition is characterized by comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the resin (B) comprises a polymer having a structural unit comprising a tertiary carbon-containing (meth) acrylate unit (a1) and an unsaturated monomer unit (B1) having an acid group.

Description

Colored curable resin composition, color filter, and display device

Technical Field

The invention relates to a colored curable resin composition, a color filter and a display device.

Background

In recent years, displays have been developed for expanding a displayable color reproduction area, and a color filter, which is an important part thereof, is also required to have a darker color. As a method for darkening a color filter, a method of increasing the colorant concentration in the color filter is exemplified, but if the colorant concentration is increased, the performance such as the pattern shape is deteriorated is not sufficient. Further, in order to have a desired color characteristic, the color filter needs to be formed to have a thick film, but when used in a liquid crystal display device, color mixing with light of adjacent pixels occurs, and thus it is not preferable to form a thick film.

For example, patent document 1 describes a colored curable resin composition containing a colorant, a resin, a predetermined polymerizable compound, a polymerization initiator, and a thiol compound, but further improvement in darkening (darkening effect) is desired.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2020 and 041154

Disclosure of Invention

Accordingly, an object of the present invention is to provide a colored curable resin composition and the like that can provide a color filter having an excellent deep color effect.

That is, the colored curable resin composition, the color filter, and the display device of the present invention have the following gist.

[1] A colored curable resin composition characterized by comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),

the resin (B) contains a polymer having a structural unit composed of a tertiary carbon-containing (meth) acrylate unit (a1) and an unsaturated monomer unit (B1) having an acid group.

[2] The colored curable resin composition according to [1], wherein the unsaturated monomer having an acid group as the above (b1) is at least 1 selected from acrylic acid and methacrylic acid.

[3] The colored curable resin composition according to [1] or [2], wherein the resin (B) has an acid value of more than 80mgKOH/g and a weight average molecular weight of 9000 or less.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant (A) contains at least a green colorant.

[5] The colored curable resin composition according to [4], wherein the green colorant is at least 1 selected from the group consisting of C.I. pigment Green 58 and C.I. pigment Green 59.

[6] The colored curable resin composition according to any one of [1] to [5], wherein the colorant (A) further comprises a yellow colorant, and the yellow colorant is at least 1 selected from the group consisting of C.I. pigment yellow 138, C.I. pigment yellow 139, C.I. pigment yellow 150, and C.I. pigment yellow 185.

[7] A color filter comprising the colored curable resin composition according to any one of [1] to [6 ].

[8] A display device comprising the color filter of [7 ].

The present invention can provide a colored curable resin composition that can provide a color filter having an excellent deep color effect.

Detailed Description

The colored curable resin composition of the present invention contains a colorant (hereinafter, sometimes referred to as a colorant (a)) and a resin (hereinafter, sometimes referred to as a resin (B)).

The colored curable resin composition of the present invention may contain a polymerizable compound (hereinafter, sometimes referred to as a polymerizable compound (C)), a polymerization initiator (hereinafter, sometimes referred to as a polymerization initiator (D)), a solvent (hereinafter, sometimes referred to as a solvent (E)), and a polymerization initiation aid (hereinafter, sometimes referred to as a polymerization initiation aid (D1)).

The colored curable resin composition of the present invention may contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

In the present invention, the dark effect means that a difference in color change occurs between the colored composition layer after the preliminary baking and the color filter after the post-baking, and the color becomes dark with respect to a predetermined film thickness.

The colored curable resin composition of the present invention is characterized by comprising a colorant (a), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the resin (B) is characterized by comprising a polymer having a structural unit composed of a tertiary carbon-containing (meth) acrylate unit (a1) and an unsaturated monomer unit (B1) having an acid group.

In the present specification, "(meth) acrylate" means at least 1 selected from acrylate and methacrylate. The same meanings are also given to "(meth) acryloyl group", "meth) acrylic acid", and the like.

In the present specification, the compounds exemplified as the respective components may be used alone or in combination of plural kinds unless otherwise specified.

< colorant (A) >)

The colored curable resin composition of the present invention contains a colorant (a), and the colorant (a) preferably contains at least a green colorant. The green colorant may be any of a pigment and a dye, and is preferably a pigment, more preferably zinc phthalocyanine, further preferably polyhalogenated zinc phthalocyanine, further preferably polychlorinated zinc phthalocyanine or polybrominated zinc phthalocyanine, and particularly preferably selected from c.i. pigment green 58 and c.i. pigment green 59.

The green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) may be subjected to, if necessary, rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, graft treatment of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like.

The green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is preferably used in the state of a dispersion liquid uniformly dispersed in a solvent, and the dispersion liquid can be obtained by mixing the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) in the solvent. A dispersant may be mixed as necessary.

The dispersant may be any of cationic, anionic, nonionic and amphoteric, and examples thereof include polyester, polyamine, acrylic and other dispersants.

These dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), AJISPER (manufactured by Ajinomoto Fine chemical Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

As the dispersant, the resin (B) (preferably, the resin (B1)) described later can be used from the viewpoint of dispersibility of the colorant and compatibility with the resin (B).

When the dispersant is used, the amount thereof is preferably 100 parts by mass or less, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solvent tends to be obtained.

The solvent is not particularly limited, and examples thereof include the same solvents as the solvent (E) in the colored curable resin composition of the present invention. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N-dimethylformamide and the like are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like are more preferable.

The amount of the solvent used is not particularly limited, and the solvent may be used so that the solid content concentration in the pigment dispersion can be adjusted to 3 to 30% by mass, more preferably 5 to 25% by mass.

The colorant (a) may contain a pigment and/or dye such as a yellow colorant and a blue colorant as the 2 nd colorant other than a green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine). The colorant (a) preferably further contains a yellow colorant.

As The pigment, there may be mentioned an organic pigment and an inorganic pigment, and there may be mentioned a compound classified as a pigment (pigment) in The color index (published by The Society of Dyers and Colourists).

Examples of the organic pigment include yellow pigments such as c.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;

c.i. pigment blue 15, 15:3, 15:4, 15:6, 60, etc.;

violet pigments of c.i. pigment violet 1, 19, 23, 29, 32, 36, 38, etc.;

green pigments other than polyhalogenated zinc phthalocyanines such as c.i. pigment green 7 and 36; and the like.

Among them, the pigment preferably contains at least 1 or more selected from green pigments other than zinc phthalocyanine, yellow pigments and blue pigments.

The green colorant (preferably a green pigment) and the blue colorant (preferably a blue pigment) are preferably c.i. pigment blue 15:3, 15:6, c.i. pigment green 7, 36. The yellow colorant (preferably a yellow pigment) is preferably selected from the group consisting of c.i. pigment yellow 138, c.i. pigment yellow 139, c.i. pigment yellow 150 and c.i. pigment yellow 185. These pigments may be used in 2 or more kinds.

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced thereto, a pigment dispersant, or the like, a graft treatment of the pigment surface with a polymer compound or the like, a micronization treatment by a sulfuric acid micronization method or the like, a cleaning treatment by an organic solvent, water, or the like for removing impurities, a removal treatment by an ion exchange method or the like for removing ionic impurities, or the like, as required. In addition, the pigment is preferably uniform in particle size. The pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by performing a dispersion treatment with the pigment dispersant.

As the pigment dispersant, commercially available surfactants can be used, and examples thereof include silicone-based, fluorine-based, ester-based, cationic-based, anionic-based, nonionic-based, amphoteric, polyester-based, polyamine-based, acrylic-based, and the like surfactants. Examples of the surfactant include, in addition to polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines, and also include, by trade name, KP (manufactured by shin-Etsu chemical Co., Ltd.), florten (manufactured by Kyoeisha chemical Co., Ltd.), Solsperse (manufactured by Lubrizol Co., Ltd.), EFKA (manufactured by BASF Japan Co., Ltd.), AJISPER (manufactured by AJIERSPER Fine chemical Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like. These may be used alone or in combination of 2 or more.

When a dispersant is used as the pigment, the amount of the dispersant used is preferably 100% by mass or less, more preferably 1 to 50% by mass, based on the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The dye is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of The dye include compounds classified as substances having a color tone other than pigments in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing guidelines (color dyeing companies). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be given. Among them, organic solvent-soluble dyes are preferable.

From the viewpoint of the deep color effect, the content of all colorants is 45.5% by mass or more, preferably 46.0% by mass or more, more preferably 46.5% by mass or more, and further preferably 65% by mass or less, more preferably 63% by mass or less, and further preferably 61% by mass or less, relative to the solid content of the colored curable resin composition.

The content of the green colorant can be appropriately adjusted to achieve a desired chromaticity. From the viewpoint of the effect of a dark color, it is preferably 35 to 99.9% by mass based on the solid content of all colorants. The lower limit of the content of the green colorant is more preferably 40% by mass or more, still more preferably 50% by mass or more, and still more preferably 60% by mass or more. The upper limit of the content of the green colorant is more preferably 98% by mass or less, still more preferably 95% by mass or less, and still more preferably 90% by mass or less.

From the viewpoint of the deep color effect, the content of the green colorant is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, even more preferably 15 to 50% by mass, and even more preferably 20 to 45% by mass, based on the solid content of the colored curable resin composition.

When the colorant contains both c.i. pigment green 59 and c.i. pigment green 58, the content ratio of c.i. pigment green 59 to c.i. pigment green 58, expressed by "content of c.i. pigment green 59: content of c.i. pigment green 58", may be in the range of 0.1 to 99.9:99.9 to 0.1, preferably 1 to 99:99 to 1. Their content ratio can be appropriately adjusted to match the desired color.

When a green pigment other than zinc phthalocyanine is contained, the amount of the green pigment other than zinc phthalocyanine used is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, further preferably 10 parts by mass or more, preferably 2000 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 100 parts by mass or less, per 100 parts by mass of zinc phthalocyanine.

The yellow colorant may be any one of a yellow pigment and a yellow dye, and is preferably a yellow pigment.

The content of all the yellow pigments is preferably 5 to 40% by mass, more preferably 10% by mass or more, further preferably 15% by mass or more, and further preferably 20% by mass or more, based on the solid content of all the colorants.

The content of all the yellow pigments is preferably 1% by mass to 30% by mass, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the solid content of all the colored curable resin compositions.

The blue colorant may be any one of a blue pigment and a blue dye, and is preferably a blue pigment.

The content of the total blue pigment is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and still more preferably 3 to 20% by mass, based on the solid content of the total colorant.

The content of all the blue pigments is preferably 1% by mass to 30% by mass, more preferably 25% by mass or less, and still more preferably 20% by mass or less, based on the solid content of all the colored curable resin compositions.

When the colorant (a) contains both a green colorant and a yellow colorant, the content of the yellow colorant is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, even more preferably 5 to 60 parts by mass, and even more preferably 8 to 40 parts by mass, based on 100 parts by mass of the green colorant.

The total amount of the colorants (a) is preferably 25 to 65% by mass, more preferably 30 to 60% by mass, and still more preferably 35 to 55% by mass, based on 100% by mass of the solid content of the colored curable resin composition.

< resin (B) >

The resin (B) used in the present invention may be an alkali-soluble resin. The resin (B) includes a polymer (B1) having a structural unit composed of a (meth) acrylate unit (a1) containing a tertiary carbon and an unsaturated monomer unit (B1) having an acid group (hereinafter, sometimes referred to as a resin (B1)).

The resin (B1) is a resin that does not contain both a monomer unit having a cyclic ether structure having 2-4 carbon atoms and an ethylenically unsaturated bond and a unit derived from the monomer unit.

The tertiary-carbon-containing (meth) acrylate ester as the tertiary-carbon-containing (meth) acrylate ester unit (a1) may be, for example, a compound represented by the following general formula (1).

CH₂＝C(R)－C(＝O)－O－C(R¹)(R²)(R³) (1)

(R represents a hydrogen atom or a methyl group¹、R²And R³Represents a monovalent organic group having a carbon atom at the bonding position with a carbon atom, R¹、R²And R³At least one of which has 1 or more hydrogen atoms on the carbon atom at the bonding position with the carbon atom. R¹、R²And R³R in (1)¹And R²、R²And R³Or R¹And R³May together form a ring).

R is as defined above¹、R²And R³The same or different, preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, yet more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.

As R¹、R²And R³Examples of the hydrocarbon group having 1 to 30 carbon atoms include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, and triacontyl groups; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 1-methylbutyl, 1-ethylpropyl, 3-methylbutyl, neopentyl, 1-dimethylpropyl, 2-methylpentyl, 3-ethylpentyl, 2-propylpentyl, 1-methylpentyl, 4-methylhexyl, 5-methylhexyl, 2-ethylhexyl, 1-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 3-ethylheptyl, 1-methylheptyl, 1-ethylhexyl, 1-propylpentyl, 1-methyloctyl, 1-ethylheptyl, 1-propylhexyl, 1-butylpentyl, 1-methylnonyl, 1-ethyloctyl, 1-propylheptyl, and 1-butylhexyl; cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-dimethylcyclohexyl, 1, 3-dimethylcyclohexyl, 1, 4-dimethylcyclohexyl, 2, 3-dimethylcyclohexyl, 2, 4-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl, 2, 6-dimethylcyclohexyl, 3, 4-dimethylcyclohexyl, 3, 5-dimethylcyclohexyl, 2-dimethylcyclohexylHexyl, 3-dimethylcyclohexyl, 4-dimethylcyclohexyl, cyclooctyl, 4-pentylcyclohexyl, 4-octylcyclohexyl and 4-cyclohexylcyclohexyl, decahydronaphthyl, norbornyl, adamantyl, bicyclo [2.2.2]An alicyclic hydrocarbon group such as octyl; phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2, 3-dimethylphenyl group, 2, 4-dimethylphenyl group, 2, 5-dimethylphenyl group, 2, 6-dimethylphenyl group, 3, 4-dimethylphenyl group, 3, 5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 1-naphthyl group, 2-naphthyl group, 6-methyl-2-naphthyl group, 5,6,7, 8-tetrahydro-1-naphthyl group, 5,6,7, 8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthracenyl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group, peryleneyl group,

And an aromatic hydrocarbon group such as a pyrenyl group. R¹、R²And R³The hydrocarbon group having 1 to 30 carbon atoms may be a combination of 2 kinds selected from the group consisting of the above-mentioned linear alkyl group, branched alkyl group, alicyclic hydrocarbon group and aromatic hydrocarbon group. Among them, preferred are linear alkyl groups, branched alkyl groups and alicyclic hydrocarbon groups, and more preferred are branched alkyl groups and alicyclic hydrocarbon groups.

R¹And R²、R²And R³Or R¹And R³Examples of the ring which may be formed together include the same groups as those mentioned as the above-mentioned alicyclic hydrocarbon group.

Specific examples of the tertiary carbon-containing (meth) acrylate ester unit (a1) include the following structural units (a 1-0) to (a 1-2).

[ formula (a 1-0), formula (a 1-1) and formula (a 1-2),

L^a01、L^a1and L^a2Each independently represents an oxygen atom or^*－O－(CH₂)_k1-CO-O-, k1 represents any integer from 1 to 7, and represents a bonding site to-CO-.

R^a01、R^a4And R^a5Each independently represents a hydrogen atom or a methyl group.

R^a02、R^a03And R^a04Each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a combination thereof.

R^a6And R^a7Each independently represents an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining these.

m1 represents any integer of 0 to 14.

n1 represents any integer of 0 to 10.

n 1' represents any integer of 0 to 3. ]

R^a01、R^a4And R^a5Preferably a hydrogen atom.

L^a01、L^a1And L^a2Preferably an oxygen atom or-O- (CH)₂)_k01-CO-O- (wherein k01 is preferably an integer of 1 to 4, more preferably 1), and more preferably an oxygen atom.

As R^a02、R^a03、R^a04、R^a6And R^a7Examples of the alkyl group in (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

R^a02、R^a03、R^a04、R^a6And R^a7The alicyclic hydrocarbon group in (b) may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl group, adamantyl group, norbornyl group, and the following groups (— represents a bonding site).

As R^a02、R^a03、R^a04、R^a6And R^a7Examples of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group in (2) include a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, a cyclohexylmethyl group, an adamantylmethyl group, an adamantyldimethyl group, and a norbornylethyl group.

R^a02、R^a03And R^a04The number of carbon atoms of the alkyl group in (1) to (6) is preferably 1 to (4), more preferably 1 to (2). R^a6And R^a7The number of carbon atoms of the alkyl group in (1) to (6) is preferably 1 to (4), and more preferably 2 to (3). R^a02、R^a03And R^a04The alicyclic hydrocarbon group (2) preferably has 5 to 12 carbon atoms, more preferably 5 to 10 carbon atoms. The total number of carbon atoms of the group obtained by combining an alkyl group and an alicyclic hydrocarbon group is preferably 18 or less.

R^a02And R^a03The alkyl group having 1 to 6 carbon atoms is preferable, the methyl group or the ethyl group is more preferable, and the methyl group is further preferable. R^a04Preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a cyclohexyl group or an adamantyl group. R^a6And R^a7The alkyl group having 1 to 6 carbon atoms is preferred, the methyl group, the ethyl group or the isopropyl group is more preferred, and the ethyl group or the isopropyl group is further preferred.

m1 is preferably an integer of 0 to 3, more preferably 0 or 1. n1 is preferably an integer of 0 to 3, more preferably 0 or 1. n 1' is preferably 0 or 1.

Examples of the structural unit (a 1-0) include structural units represented by any of formulae (a 1-0-1) to (a 1-0-12) and (a 1-0-13) to (a 1-0-24).

Examples of the structural unit (a 1-1) include structural units represented by any of formulae (a 1-1-1) to (a 1-1-4) and (a 1-1-5) to (a 1-1-8).

Examples of the structural unit (a 1-2) include structural units represented by any of the formulae (a 1-2-1) to (a 1-2-6) and (a 1-2-7) to (a 1-2-12).

Among them, the tertiary carbon-containing (meth) acrylate ester unit (a1) is preferably a structural unit represented by formula (a 1-0), more preferably structural units represented by formulae (a 1-0-1) to (a 1-0-24), still more preferably structural units represented by formulae (a 1-0-13) to (a 1-0-24), and still more preferably structural units represented by formula (a 1-0-13).

The content of the tertiary carbon-containing (meth) acrylate unit (a1) is preferably not less than 1% by mass and less than 100% by mass of the structural unit of the resin (B1). The resin (B1) may contain a polymer containing a tertiary carbon-containing (meth) acrylate unit (a1) in an amount of more than 80 mass% based on 100 mass% of the structural unit of the resin (B1).

The unsaturated monomer having an acid group as the unsaturated monomer unit (b1) having an acid group is preferably at least 1 selected from acrylic acid and methacrylic acid, and more preferably acrylic acid.

The content of the unsaturated monomer unit (B1) having an acid group is preferably more than 0% by mass and not more than 99% by mass in 100% by mass of the structural unit of the resin (B1).

The above resin (B) (preferably resin (B1)) preferably has an acid value of more than 80mgKOH/g and a weight average molecular weight of 9000 or less.

The acid value of the resin (B1) is preferably more than 80mgKOH/g, more preferably 85mgKOH/g or more, still more preferably 95mgKOH/g or more, yet more preferably 105mgKOH/g or more, preferably 300mgKOH/g or less, still more preferably 250mgKOH/g or less, and still more preferably 200mgKOH/g or less. The acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be determined by titration using an aqueous potassium hydroxide solution, for example.

The weight average molecular weight of the resin (B1) in terms of polystyrene is preferably 9000 or less, more preferably 8500 or less, still more preferably 8000 or less, still more preferably 7500 or less, preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more, and still more preferably 2500 or more.

The content of the resin (B1) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, and still more preferably 60 to 90% by mass, based on 100% by mass of the resin (B). The content of the resin (B1) is preferably 1 to 50% by mass, more preferably 2 to 45% by mass, even more preferably 5 to 40% by mass, and even more preferably 8 to 35% by mass, based on 100% by mass of the solid content of the colored curable resin composition.

The resin (B) may contain a resin (B2) (hereinafter, sometimes referred to as resin (B2)) different from the resin (B1). Examples of the resin (B2) include the following resins [ K1] to [ K6 ].

A resin [ K1] which is a copolymer having a structural unit derived from at least 1 (a2) (hereinafter sometimes referred to as "(a 2)") selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer (b2) (hereinafter sometimes referred to as "(b 2)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

a resin [ K2] which is a copolymer having a structural unit derived from (a2), a structural unit derived from (b2), and a structural unit derived from a monomer (c2) copolymerizable with (a2) (wherein (a2) and (b2) are different) (hereinafter sometimes referred to as "(c 2)");

a resin [ K3] having a copolymer of a structural unit derived from (a2) and a structural unit derived from (c 2);

a resin [ K4] which is a copolymer comprising a structural unit obtained by adding (b2) to a structural unit derived from (a2) and a structural unit derived from (c 2);

a resin [ K5] which is a copolymer comprising a structural unit obtained by adding (a2) to a structural unit derived from (b2) and a structural unit derived from (c 2);

the resin [ K6] is a copolymer comprising a structural unit obtained by adding (a2) and further adding a carboxylic acid anhydride to a structural unit derived from (b2) and a structural unit derived from (c 2).

Specific examples of (a2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid; carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [ 2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [ 2- (meth) acryloyloxyethyl ] ester; and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid. Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

(b2) For example, the polymerizable compound has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b2) The monomer preferably contains a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of (b2) include a monomer (b 2-1) (hereinafter sometimes referred to as "(b 2-1)") having an oxetanyl group and an ethylenically unsaturated bond, a monomer (b 2-2) (hereinafter sometimes referred to as "(b 2-2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b 2-3) (hereinafter sometimes referred to as "(b 2-3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

Examples of (b 2-1) include a monomer (b 2-1-1) (hereinafter sometimes referred to as "(b 2-1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a monomer (b 2-1-2) (hereinafter sometimes referred to as "(b 2-1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

Examples of (b 2-1-1) include glycidyl (meth) acrylate,. beta. -methylglycidyl (meth) acrylate,. beta. -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,. alpha. -methyl-o-vinylbenzyl glycidyl ether,. alpha. -methyl-m-vinylbenzyl glycidyl ether,. alpha. -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of (b 2-1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000, (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400, (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100, (manufactured by Daicel Co., Ltd.)), compounds represented by the formula (I), and compounds represented by the formula (II).

[ formula (I) and formula (II) wherein R^aAnd R^bRepresents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^aAnd X^bRepresents a single bond, — R^c－、*－R^c－O－、*－R^c-S-or R^c－NH-。

R^cRepresents an alkanediyl group having 1 to 6 carbon atoms.

Denotes the bonding site to O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

As R^aAnd R^bPreferred examples thereof include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferred examples thereof include a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X^aAnd X^bPreferred examples thereof include a single bond, methylene, ethylene and-CH₂-O-and-CH₂CH₂－O－More preferably, a single bond and a-CH₂CH₂-O- (. indicates a bonding site to O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulae (I-1) to (I-15). Among them, preferred are compounds represented by formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formulae (I-11) to (I-15), and more preferred are compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, preferred are compounds represented by the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9) or the formulae (II-11) to (II-15), and more preferred are compounds represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of 2 or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [ the compound represented by the formula (I): the compound represented by the formula (II) ] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

As (b 2-2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b 2-2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, and 3-ethyl-3-acryloxyethyloxetane.

As (b 2-3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b 2-3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V #150, manufactured by Osaka Organischen chemical industries, Ltd.), and tetrahydrofurfuryl methacrylate.

The compound (b2) is preferably (b 2-1) in view of enabling the obtained color filter to have higher reliability such as heat resistance and chemical resistance. Further, (b 2-1-2) is more preferable in that the colored curable resin composition has excellent storage stability.

Examples of (c2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] meth) acrylate^2,6]Decan-8-yl ester (which is known as "dicyclopentyl (meth) acrylate" as a common name in the art, and may be referred to as "tricyclodecyl (meth) acrylate" in some cases), and tricyclo (meth) acrylate [5.2.1.0^2,6](meth) acrylate esters such as decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylate dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo-unsaturated compounds such as bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene and the like;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among them, 2-hydroxyethyl (meth) acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

In the resin [ K1], the ratio of the structural units derived from the respective units is preferably 2 to 60 mol% of the structural unit derived from (a2), 40 to 98 mol% of the structural unit derived from (b2), more preferably 10 to 50 mol% of the structural unit derived from (a2), and 50 to 90 mol% of the structural unit derived from (b2, all of the structural units constituting the resin [ K1 ].

When the ratio of the structural units of the resin [ K1] is within the above range, the colored curable resin composition is excellent in storage stability, developability in forming a colored pattern, and solvent resistance of the obtained color filter.

The resin [ K1] can be produced, for example, by referring to the method described in "Experimental method for Polymer Synthesis" (published by Otsuka institute of Engineers, 1 st edition, chemical Co., Ltd., 1972, 3 months and 1 days), and the cited documents described in the above documents.

Specifically, there can be mentioned a method comprising charging predetermined amounts of (a2) and (b2), a polymerization initiator, a solvent and the like into a reaction vessel, replacing oxygen with nitrogen, for example, to prepare a deoxygenated atmosphere, and heating and maintaining the temperature while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include solvents that dissolve the monomers, and solvents described below as the solvent (E) of the colored curable resin composition of the present invention.

The copolymer obtained may be used as it is, as a solution after the reaction, as a solution after concentration or dilution, or as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention, and therefore, the production process of the colored curable resin composition of the present invention can be simplified.

In the resin [ K2], the ratio of the structural units derived from the respective units is preferably 2 to 45 mol% of the structural unit derived from (a2), 2 to 95 mol% of the structural unit derived from (b2), 1 to 65 mol% of the structural unit derived from (c2), more preferably 5 to 40 mol% of the structural unit derived from (a2), 5 to 80 mol% of the structural unit derived from (b2), and 5 to 60 mol% of the structural unit derived from (c2, among all the structural units constituting the resin [ K2 ].

When the ratio of the structural units of the resin [ K2] is within the above range, the colored curable resin composition is excellent in storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the obtained color filter.

The resin [ K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

In the resin [ K3], the ratio of the structural units derived from the respective units is preferably 2 to 60 mol% of the structural unit derived from (a2), 40 to 98 mol% of the structural unit derived from (c2), more preferably 10 to 50 mol% of the structural unit derived from (a2), and 50 to 90 mol% of the structural unit derived from (c2, all of the structural units constituting the resin [ K3 ].

The resin [ K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [ K1 ].

The resin [ K4] can be produced by obtaining a copolymer of (a2) and (c2) and adding a cyclic ether having 2 to 4 carbon atoms of (b2) to a carboxylic acid and/or a carboxylic acid anhydride of (a 2).

First, a copolymer of (a2) and (c2) was produced in the same manner as in the method described for producing resin [ K1 ]. In this case, the ratio of the structural units derived from each unit is preferably the same as the ratio recited in resin [ K3 ].

Then, a cyclic ether having 2 to 4 carbon atoms of (b2) is reacted with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a2) in the copolymer.

After the production of the copolymer of (a2) and (c2), the atmosphere in the flask is subsequently replaced with air from nitrogen, and (b2), a catalyst for the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether (e.g., tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) are placed in the flask and reacted at 60 to 130 ℃ for 1 to 10 hours, for example, to produce a resin [ K4 ].

(b2) The amount of (b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). When the content is within this range, the storage stability of the colored curable resin composition, the developability in forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern are well balanced. The cyclic ether is highly reactive and (b2) used for the resin [ K4] is preferably (b 2-1), more preferably (b 2-1-1), from the viewpoint that unreacted (b2) hardly remains.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a2), (b2) and (c 2). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a2), (b2) and (c 2).

The reaction conditions such as the charging method, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facilities, the amount of heat generated by polymerization, and the like.

As the first stage, a copolymer of (b2) and (c2) was obtained in the same manner as in the above-described method for producing the resin [ K1] [ K5 ]. As described above, the copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a substance taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b2) and (c2) is preferably 5 to 95 mol% of the structural unit derived from (b2), 5 to 95 mol% of the structural unit derived from (c2), more preferably 10 to 90 mol% of the structural unit derived from (b2), and 10 to 90 mol% of the structural unit derived from (c2, based on the total mol number of all the structural units constituting the copolymer.

Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride of (a2) with the cyclic ether derived from (b2) of the copolymer of (b2) and (c2) under the same conditions as the process for producing the resin [ K4 ].

The amount of (a2) to be used in the reaction with the copolymer is preferably 5 to 80 moles per 100 moles of (b 2). The cyclic ether is highly reactive and (b2) used for the resin [ K5] is preferably (b 2-1), more preferably (b 2-1-1), from the viewpoint that unreacted (b2) hardly remains.

The resin [ K6] is a resin obtained by further reacting a carboxylic acid anhydride with the resin [ K5 ]. Reacting a carboxylic anhydride with a hydroxyl group produced by the reaction of the cyclic ether and the carboxylic acid or carboxylic anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol based on 1 mol of the amount of (a 2).

Specific examples of the resin (B2) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and 3, 4-epoxytricyclo [5.2.1.0 ] acrylate^2,6]Resins such as decyl ester/(meth) acrylic acid copolymers [ K1]](ii) a Glycidyl (meth) acrylate/benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]Resins such as decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Resins such as (meth) acrylate/(meth) acrylic acid copolymers, benzyl (meth) acrylate/(meth) acrylic acid copolymers, and styrene/(meth) acrylic acid copolymers [ K3](ii) a A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and a resin obtained by adding tricyclodecyl (meth) acrylate/(meth) acrylic acid benzyl ester/(meth) acrylic acid copolymer to (meth) acrylic acidResins obtained from glycidyl esters of acids [ K4](ii) a Resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) [ K5](ii) a Resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecanyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by further reacting tetrahydrophthalic anhydride [ K6]And the like.

Among them, as the resin (B2), the resin [ K1] and the resin [ K2] are preferable, and the resin [ K1] is particularly preferable.

The weight average molecular weight of the resin (B2) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, still more preferably 5000 to 30000, and still more preferably 9500 to 30000. When the molecular weight is within the above range, the unexposed portion tends to have high solubility in a developer, and the pattern obtained tends to have a high residual film ratio and high hardness.

The molecular weight distribution [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B2) is preferably 1.1 to 6, more preferably 1.2 to 4.

The solid acid value of the resin (B2) is preferably 85mgKOH/g or more, more preferably 100mgKOH/g or more, and still more preferably 110mgKOH/g or more. The solid acid value is preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, and still more preferably 160mgKOH/g or less. When the solid acid value of the resin (B2) is within the above range, a colored pattern having a good shape tends to be obtained from the colored curable resin composition. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin, and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin (B2) is preferably 0 to 60% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 40% by mass, based on 100% by mass of the resin (B).

The content of the resin (B2) is preferably 1 to 40% by mass, more preferably 2 to 35% by mass, and still more preferably 3 to 30% by mass, based on 100% by mass of the solid content of the colored curable resin composition.

The content of the resin (B) (preferably the content of the resin (B1) and the resin (B2)) is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 15 to 30 mass% of the solid content 100 mass% of the colored curable resin composition. When the content of the resin (B) is within the above range, the solubility of the unexposed portion in the developer tends to be high.

< polymerizable Compound (C) >)

The polymerizable compound (C) is a compound that can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D). Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond and a hydroxyl group.

Specific examples of the polymerizable compound (C) include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene glycol-modified pentaerythritol tri (meth) acrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane di (meth) acrylate, ethylene glycol-modified glycerol di (meth) acrylate, propylene glycol-modified glycerol di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ethylene glycol-modified ditrimethylolpropane tri (meth) acrylate, propylene glycol-modified ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol mono (meth) acrylate, and mixtures thereof, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and the like.

The content of the polymerizable compound (C) is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total amount of solid components in the colored curable resin composition.

< polymerization initiator (D) >)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid, or the like under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. As the polymerization initiator generating active radicals, for example, an alkylbenzene ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound can be cited.

The O-acyloxime compound is a compound having a partial structure represented by formula (d 1). Hereinafter, the bonding site is denoted.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxocyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, and N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-imine 1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (both of which are available from BASF corporation), N-1919 (available from ADEKA corporation), and PBG-327 (available from Changzhou powerful electron new material Co., Ltd.) can also be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, and more preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine. When these O-acyloxime compounds are used, a color filter having high luminance can be obtained.

The above-mentioned alkylphenone compound has a partial structure represented by the formula (d2) or a partial structure represented by the formula (d 3). In the partial structure of these, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [ 4- (4-morpholinyl) phenyl ] butan-1-one. Commercially available products such as Irgacure 369, 907, and 379 (all of which are manufactured by BASF corporation) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [ 4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, and benzildimethylketal.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d 2).

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

Examples of the biimidazole compound include 2,2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetraphenylbiimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (alkoxyphenyl) biimidazole, 2 '-bis (2-chlorophenyl) -4, 4', 5,5 '-tetrakis (dialkoxyphenyl) biimidazole, 2' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent application laid-open No. 48-38403 and Japanese patent application laid-open No. 62-174204), and biimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carboalkoxy group (カルボアルコキシ group) (see, for example, Japanese patent application laid-open No. 7-10913).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

Examples of the acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyltoluenesulfonate and benzoin toluenesulfonate.

As the polymerization initiator (D), a polymerization initiator containing at least 1 selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound is preferable, and a polymerization initiator containing an O-acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the sensitivity can be increased and the exposure time can be shortened, so that the productivity of the color filter can be improved.

< polymerization initiation assistant (D1) >)

The polymerization initiation aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator (D). When the polymerization initiator (D1) is contained, it is used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Among them, a thioxanthone compound is preferable. More than 2 polymerization initiation aids (D1) may be contained.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) may also be used.

Examples of the alkoxyanthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 9, 10-dibutoxyanthracene, and 2-ethyl-9, 10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylsulfanylacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.

The content of the polymerization initiator aid (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C1). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with further high sensitivity, and the productivity of the color filter tends to be improved.

< solvent (E) >

The colored curable resin composition of the present invention preferably contains a solvent (E). Examples of the solvent (E) include an ester solvent (a solvent containing-COO-, an ether solvent (a solvent containing-O-) other than the ester solvent, an ether ester solvent (a solvent containing-COO-and-O-), a ketone solvent (a solvent containing-CO-) other than the ester solvent, an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-di-n

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, and the like, Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin, and the like.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene, and the like.

Examples of the amide solvent include N, N-dimethylformamide, N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) may be used in combination of 2 or more.

From the viewpoint of coatability and drying properties, an organic solvent having a boiling point of 120 to 180 ℃ at 1atm is preferable. Of these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

< leveling agent (F) >

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF 46, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan contract Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by AGC (Co., Ltd.), Uxu nitro (manufactured by Asahi corporation) and E5844 (manufactured by Damiki chemical research).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443 (manufactured by DIC Co., Ltd.).

The content of the leveling agent (F) is, for example, 0.001 to 0.2 mass%, preferably 0.002 to 0.1 mass%, and more preferably 0.005 to 0.05 mass% with respect to the total amount of the colored curable resin composition. The content of the pigment dispersant is not included in the content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< method for producing dispersion liquid >

The colorant (a) may be dispersed in a dispersant and a solvent (E) to prepare a dispersion.

The dispersant is preferably one or both of an acrylic dispersant and a resin (B1), and more preferably both of an acrylic dispersant and a resin (B1).

The content of the colorant (A) is preferably 1 to 25% by mass, more preferably 2 to 20% by mass, based on 100% by mass of the dispersion.

The content of the resin (B1) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, based on 100% by mass of the dispersion.

The content of the acrylic dispersant is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on 100% by mass of the dispersion.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared by containing the colorant (a), the resin (B), the polymerizable compound (C), and the polymerization initiator (D), and mixing the solvent (E), the leveling agent (F), the polymerization initiation aid (D1), and other components as needed.

The colorant (a) may be mixed as the dispersion liquid.

< method for manufacturing color filter >

Examples of the method for producing a color filter from the colored curable resin composition of the present invention include a photolithography method, an ink-jet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film, which is a cured film of the colored composition layer, can be formed without using a photomask and/or without performing development at the time of exposure. The color filter of the present invention can be obtained by prebaking of the curable color resin composition (colored composition layer), exposure of the colored composition layer (colored coating film), development of the colored coating film (colored pattern), and postbaking of the colored pattern, and can be obtained by postbaking of the colored coating film while omitting development of the colored coating film as necessary.

As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. Further, as the substrate, a substrate subjected to surface treatment with 1,1,1,3,3, 3-hexamethyldisilazane or the like may be used.

The formation of each color pixel by photolithography can be performed by using a known or conventional apparatus and conditions. For example, the following can be used.

First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent, thereby drying the composition to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method.

The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes.

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the colored composition layer is exposed to light through a photomask for forming a target colored pattern to obtain a colored coating film. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, the light source includes a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

In order to uniformly irradiate parallel light rays to the entire exposure surface and perform precise alignment of the photomask and the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner (proximity exposure machine) or a stepper (reduction projection exposure machine).

The exposed colored coating film is brought into contact with a developer to develop the colored coating film, thereby forming a colored pattern on the substrate. The unexposed portion of the colored coating film is dissolved in a developer and removed by development. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may contain a surfactant.

The developing method may be any of spin immersion, spraying, and the like. Further, the substrate can be inclined at an arbitrary angle during development.

After development, washing with water is preferred.

Further, the obtained colored pattern is preferably subjected to post-baking. The post-drying temperature is preferably 80-250 ℃, more preferably 100-250 ℃, further preferably 150-250 ℃, and further preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 120 minutes, further preferably 10 to 60 minutes, and further preferably 10 to 30 minutes.

The thickness of the obtained colored coating film or colored pattern affects adjacent pixels, and therefore is preferably as thin as possible. In particular, when the thickness is thick, light from the light source may leak through 2 or more color pixels when the liquid crystal panel is manufactured, and when the panel is viewed from an oblique side, the color may be lost. The thickness of the colored coating film or the colored pattern is, for example, preferably 4 μm or less or 3 μm or less, more preferably 2.8 μm or less, still more preferably 2.5 μm or less, and still more preferably 2.3 μm or less. The lower limit of the film thickness of the colored coating film or the colored pattern is not particularly limited, but is usually 0.1 μm or more, preferably 0.2 μm or more, 0.5 μm or more, or 1 μm or more, and may be 1.5 μm or more.

The color filter is formed so that the film thickness after post-baking at 230 ℃ for 30 minutes is 1 to 4 μm (preferably 1 to 3 μm, more preferably 2.8 μm or less, further preferably 2.5 μm or less, and further preferably 2.3 μm or less).

By using the colored curable resin composition of the present invention, a color filter having an excellent deep color effect can be produced. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) or a solid-state imaging element.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and it is needless to say that the present invention can be carried out with appropriate modifications within the scope that can be adapted to the gist described above and below, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

Synthesis example 1

100 parts by mass of propylene glycol monomethyl ether acetate was charged into a flask equipped with a stirring blade, a reflux condenser, a thermometer and a dropping funnel, and the flask was heated to 90 ℃. A solution prepared by mixing 81 parts by mass of t-butyl acrylate, 19 parts by mass of acrylic acid, 15 parts by mass of azobisisobutyronitrile and 54 parts by mass of propylene glycol monomethyl ether acetate was continuously dropped into the flask through a dropping funnel. The temperature in the flask during the dropwise addition of the mixed solution was maintained at 90. + -. 1 ℃ and the dropwise addition was terminated over 3 hours. After completion of the dropwise addition, the reaction was carried out for 3 hours while the internal temperature of the flask was set to 90. + -. 1 ℃ and then the reaction was carried out for 1.5 hours while the internal temperature of the flask was increased to 105 to 110 ℃ to obtain a copolymer (resin B1) solution (hereinafter, sometimes referred to as a resin solution (B1)) having a solid content of 40.3 mass%. The weight-average molecular weight Mw of the resulting copolymer was 6100, and the acid value of the solid portion was 131 mgKOH/g.

Synthesis example 2

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to a nitrogen atmosphere, and 362 parts by mass of propylene glycol monomethyl ether acetate was added thereto and heated to 80 ℃ while stirring. Then, 58 parts by mass of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise over 5 hours^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]A mixed solution of 167 parts by mass of a mixture of decane-9-yl esters (containing 1:1 in terms of molar ratio), 65 parts by mass of 2-ethylhexyl acrylate, and 111 parts by mass of propylene glycol monomethyl ether acetate. On the other hand, a mixed solution of 27 parts by mass of 2, 2-azobis (2, 4-dimethylvaleronitrile) dissolved in 210 parts by mass of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 80 ℃ for 5.5 hours and then cooled to room temperature to obtain a copolymer (resin B2) solution (hereinafter, sometimes referred to as a resin solution (B2)) having a B-type viscosity (23 ℃) of 43 mPas and a solid content of 29.8 mass%. The resulting copolymer had an acid value of the solid content of 149mgKOH/g, a weight-average molecular weight Mw of 11220 and a dispersity of 2.25.

The polystyrene-equivalent weight average molecular weight Mw and number average molecular weight Mn of the resin obtained in the above synthesis example were measured by GPC under the following conditions.

A device; HLC-8120 GPC (manufactured by Tosoh corporation)

A column; TSK-GELG 2000HXL

Column temperature; 40 deg.C

A solvent; THF (tetrahydrofuran)

A flow rate; 1.0mL/min

Detecting the concentration of the solid component in the liquid; 0.001 to 0.01% by mass

Sample size; 50 μ L

A detector; RI (Ri)

A calibration standard substance; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

[ preparation of Dispersion ]

The dispersions (A-1) to (A-3) were prepared by mixing the following components and sufficiently dispersing the pigment by a bead mill. The resin solutions (B1) to (B2) were used as the resins (B1) to (B2).

[ preparation of Dispersion (A-1) ]

[ preparation of Dispersion (A-2) ]

[ preparation of Dispersion (A-3) ]

Example 1 and comparative example 1

[ preparation of colored curable resin composition ]

The components described in table 1 were mixed to obtain a colored curable resin composition.

[ Table 1]

[ Table 1]

The ingredients in table 1 are as follows. The usage amounts in the table represent the usage amounts of the following components.

Dispersion liquids (A-1) to (A-3) Dispersion liquids prepared as described above

Resin (B1) copolymer solution obtained in Synthesis example 1

Resin (B2) copolymer solution obtained in Synthesis example 2

The polymerizable compound (C) was dipentaerythritol polyacrylate (A-9570W, manufactured by Newzhongcun chemical industry Co., Ltd.)

A polymerization initiator (D) Irgacure (registered trademark) OXE-03; manufactured by BASF corporation; a compound represented by the formula (d 1-24)

Solvent (E) propylene glycol monomethyl ether acetate

Leveling agent (F) polyether-modified Silicone oil (SH 8400; propylene glycol monomethyl ether acetate solution having a solid content of 10% manufactured by Dow Corning Toray Co., Ltd.)

< production of color Filter >

The colored curable resin composition was applied onto a 2-inch square glass substrate (EAGLE XG; manufactured by CORNING corporation) by a spin coating method, and then pre-baked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the substrate on which the colored composition layer was formed and a photomask made of quartz glass were placed at an interval of 100 μm in an exposure apparatus (TME-150 RSK; manufactured by TOPCON, Inc.) under an atmospheric atmosphere at 150mJ/cm²The exposure amount (365nm basis) of (A) was irradiated with light. As the photomask, a photomask in which a 50 μm line and space pattern (line and space pattern) was formed was used. The colored coating after light irradiation is immersed and developed in an aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 DEG CThe resultant was washed with water for 60 seconds, and post-baked at 230 ℃ for 20 minutes in an oven to obtain a color filter.

[ measurement of film thickness ]

The film thickness FT (. mu.m) of the obtained color filter was measured using a film thickness measuring apparatus (DEKTAK3, manufactured by Japan vacuum technology, Ltd.).

[ measurement of color ]

The spectral spectrum of the obtained color filter was measured using a colorimeter (OSP-SP-200; manufactured by Olympus corporation), and xy chromaticity coordinates (x, y) in the CIE XYZ color system were measured using a characteristic function of a C illuminant. Xy chromaticity coordinates of the pre-baked colored composition layer and the post-baked color filter were measured, and Δ x and Δ y were calculated according to the following formulas. When Δ x and Δ y were obtained, the film thicknesses of example 1 and comparative example 1 were the same.

Δ x ═ x value of (post-bake color filter) - (pre-bake color composition layer)

Δ y ═ y (y value of color filter after post baking) - (y value of coloring composition layer after pre baking)

For example, in the green region, it can be said that the larger the absolute values of Δ x and Δ y, the higher the dark effect from after prebaking to after-baking.

Industrial applicability

The colored curable resin composition of the present invention can be preferably used for the production of color filters, display devices, and solid-state imaging devices.

Claims (8)

1. A colored curable resin composition characterized by comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),

the resin (B) includes a polymer having a structural unit composed of a tertiary carbon-containing (meth) acrylate unit (a1) and an unsaturated monomer unit (B1) having an acid group.

2. The colored curable resin composition according to claim 1, wherein the unsaturated monomer having an acid group as the (b1) is at least 1 selected from acrylic acid and methacrylic acid.

3. The colored curable resin composition according to claim 1 or 2, wherein the resin (B) has an acid value of more than 80mgKOH/g and a weight average molecular weight of 9000 or less.

4. The colored curable resin composition according to any one of claims 1 to 3, wherein the colorant (A) comprises at least a green colorant.

5. The colored curable resin composition according to claim 4, wherein the green colorant is at least 1 selected from the group consisting of C.I. pigment Green 58 and C.I. pigment Green 59.

6. The colored curable resin composition according to any one of claims 1 to 5, wherein the colorant (A) further comprises a yellow colorant which is at least 1 selected from the group consisting of C.I. pigment yellow 138, C.I. pigment yellow 139, C.I. pigment yellow 150 and C.I. pigment yellow 185.

7. A color filter comprising the colored curable resin composition according to any one of claims 1 to 6.

8. A display device comprising the color filter of claim 7.