KR102375638B1 - Colored curable resin composition - Google Patents

Abstract

The colored curable resin composition which provides the color filter which has favorable heat resistance and favorable brightness is provided.
A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colorant (A) comprises a blue pigment (A1) and CI acid red 52; Colored curable resin composition whose content of CI acid red 52 is 0.1-10 mass parts with respect to 100 mass parts of blue pigments (A1). It is preferable that the colorant (A) further contains a blue or purple dye (A2).

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

The color filter formed from a colored curable resin composition is used for display apparatuses, such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel, and the color filter which has favorable brightness, favorable contrast, and favorable resolution was calculated|required. In order to realize a color filter having good brightness, good contrast, and good resolution, a colored curable resin composition containing a dye as a colorant has been studied.

In Patent Document 1, as a coloring agent, C.I. Pigment Blue 15:6 and C.I. A colored curable resin composition comprising Acid Red 52 and a dye represented by the following formula, C.I. The content of Acid Red 52, C.I. The colored curable resin composition which is 14.7 mass parts with respect to pigment blue 15:6 100 mass parts is described.

Japanese Patent Laid-Open No. 2013-144724

The color filter formed from said colored curable resin composition could not necessarily fully satisfy both heat resistance and brightness.

The present invention includes the following inventions.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), wherein the colorant (A) comprises a blue pigment (A1) and C.I. Acid Red 52, and C.I. Colored curable resin composition whose content of acid red 52 is 0.1-10 mass parts with respect to 100 mass parts of blue pigments (A1).

[2] The colored curable resin composition according to [1], wherein the colorant (A) further contains a blue or purple dye (A2).

[3] The content of the blue or purple dye (A2) is C.I. The colored curable resin composition as described in [2] which is 80-10000 mass parts with respect to 100 mass parts of acid red 52.

[4] The content of the blue or purple dye (A2) is C.I. The colored curable resin composition as described in [3] which is 80-1000 mass parts with respect to 100 mass parts of acid red 52.

[5] The blue pigment (A1) is C.I. The colored curable resin composition according to any one of [1] to [4] containing Pigment Blue 15:6.

[6] The blue pigment (A1) is C.I. The colored curable resin composition according to any one of [1] to [4], which consists only of Pigment Blue 15:6.

[7] Triarylmethane dyes, blue pigments (A1) and C.I. A colorant comprising Acid Red 52, wherein the triarylmethane dye is a polymer.

[8] The blue pigment (A1) is C.I. The colorant according to [7], comprising Pigment Blue 15:6.

[9] The blue pigment (A1) is C.I. The coloring agent according to [7], which consists only of Pigment Blue 15:6.

[10] A colored curable resin composition comprising the colorant according to any one of [7] to [9], a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

[11] A polymer comprising a dye represented by the formula (A7) or a structural unit derived from a dye represented by the formula (A7), a blue pigment (A1) and C.I. A colorant comprising Acid Red 52.

[In formula (A7),

g represents an arbitrary natural number.

G ^{g -} represents a g-valent anion.

D represents the heteroaromatic hydrocarbon group which may have a substituent.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group, and included in the alkyl group - CH ₂ - may be substituted with -O-.

R ^21A and R ^22A each independently represent an optionally substituted amino group.]

[12] The blue pigment (A1) is C.I. The colorant according to [11], comprising Pigment Blue 15:6.

[13] The blue pigment (A1) is C.I. The coloring agent according to [11], which consists only of Pigment Blue 15:6.

[14] A colored curable resin composition comprising the colorant according to any one of [11] to [13], a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

[15] A color filter formed of the colored curable resin composition according to any one of [1] to [6], [10] and [14].

[16] A display device including the color filter according to [15].

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the color filter which has favorable heat resistance and favorable brightness can be manufactured.

The colored curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D).

It is preferable that the colored curable resin composition of this invention contains at least 1 chosen from a solvent (E) and a leveling agent (F).

The colored curable resin composition of this invention may also contain the polymerization initiation adjuvant (D1).

<Colorant (A)>

The colorant (A) is a blue pigment (A1) and C.I. Contains Acid Red 52.

C.I. It is preferable that content of acid red 52 is 0.1-10 mass parts with respect to 100 mass parts of blue pigments (A1), It is more preferable that it is 0.1-8 mass parts, It is more preferable that it is 1-8 mass parts.

The coloring agent (A) may contain the blue or purple dye (A2) (Hereinafter, it may be called "dye (A2)."). The colorant (A) is a pigment different from the blue pigment (A1) (hereinafter, sometimes referred to as “pigment (Ad)”), a dye (Ac) different from the blue or purple dye (A2) (hereinafter, “ dye (Ac)") may also be included.

In addition, in this application, "C.I." means a color index (C.I.).

<Blue pigment (A1)>

As the blue pigment (A1), C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, preferably C.I. Pigment Blue 15:3 and 15:6, more preferably C.I. Pigment Blue 15:6.

The blue pigment (A1) may contain 2 or more types.

The blue pigment (A1) is C.I. Pigment Blue 15:6 is preferred, and C.I. It is more preferable to consist only of Pigment Blue 15:6.

<Dye (A2)>

A blue or purple dye means the dye which has a maximum absorption wavelength in the range of 560 nm or more and 650 nm or less in a chloroform solution. The blue or purple dye is preferably a dye having a maximum absorption wavelength in a range of 580 nm or more and 650 nm or less, and more preferably a dye having a maximum absorption wavelength in a range of 600 nm or more and 645 nm or less.

The blue or purple dye (A2) is a dye represented by a xanthene dye (A3), a triarylmethane dye (A4), a tetraazaporphyrin dye (A5), an anthraquinone dye (A6) and a formula (A7) (hereinafter, It is preferable that it is at least one selected from the group which consists of dye (A7).

It is more preferably at least one selected from the group consisting of a xanthene dye (A3), a triarylmethane dye (A4) and a dye (A7),

It is more preferable that it is at least one selected from the group which consists of a triarylmethane dye (A4) and a dye (A7).

The dye (A2) may contain 2 or more types.

A xanthene dye (A3) is a dye containing the compound which has a xanthene skeleton in a molecule|numerator.

Examples of the xanthene dye (A3) include the compounds described below. In the following formula, R ²⁶ and R ⁴⁰ each represent a 2-ethylhexyl group.

As the xanthene dye (A3), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH/C” manufactured by Chugai Chemical Co., Ltd., “Rhodamin 6G” manufactured by Daoka Chemical Industry Co., Ltd.) ) can also be included. Moreover, as a starting material, a commercially available xanthene dye can also be synthesize|combined with reference to Unexamined-Japanese-Patent No. 2010-32999.

A triarylmethane dye (A4) is a dye containing the compound which has a triarylmethane skeleton in a molecule|numerator. As the triarylmethane dye (A4), for example,

C.I. Acid Violet (Hereinafter, the description of C.I. Acid Violet is omitted and only the number is described.) 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72,

C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 38, 48, 75, 83, 84, 86, 88, 90, 90:1, 91, 93, 93:1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269,

C.I. Basic Blue 7, 81, 83, 88, 89,

C.I. Basic Violet 2,

C.I. Direct Blue 1, 3, 28, 29, 41, 42, 47, 52, 55,

C.I. food violet 3,

C.I. Mordant Violet 1, 1:1, 3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49

and the like.

As triarylmethane dye (A4), the compound described below is also mentioned.

The tetraazaporphyrin dye (A5) is a dye containing a compound having a tetraazaporphyrin skeleton in a molecule. Moreover, when the tetraazaporphyrin dye is an acid dye or a basic dye, you may form the salt with arbitrary cations or anions.

Examples of the tetraazaporphyrin dye include the compounds described below.

Anthraquinone dye (A6) is a dye containing the compound which has an anthraquinone skeleton in a molecule|numerator.

As anthraquinone dye (A6), for example,

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,

C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,

C.I. Acid Violet 34

C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112

C.I. Disperse Violet 26, 27,

C.I. Disperse Blue 1, 14, 56, 60

C.I. direct blue 40,

C.I. modern blue 8

and the like.

Examples of the anthraquinone dye (A6) include compounds described below.

As dye (A7), the compound represented by Formula (A7), and its tautomer are mentioned.

[In formula (A7),

g represents an arbitrary natural number.

G ^{g -} represents a g-valent anion.

D represents the heteroaromatic hydrocarbon group which may have a substituent.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group, and included in the alkyl group - CH ₂ - may be substituted with -0-.

R ^21A and R ^22A each independently represent an optionally substituted amino group.]

As the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A , methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclo Hexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1 -(adamantan-1-yl) alkane-1-yl, norbornyl, methyl norbornyl and isobornyl, and other alkyl groups having 1 to 20 carbon atoms. Preferably it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, More preferably, it is a C1-C4 alkyl group.

-CH ₂ - contained in the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A may be substituted with -O-.

As a group in which -CH ₂ - contained in the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A is substituted with -O-, specifically, The same flag can be lifted. Preferably, -CH ₂ - contained in an alkyl group having 1 to 10 carbon atoms is a group substituted with -O-, more preferably -CH ₂ - contained in an alkyl group having 1 to 6 carbon atoms is -O- It is a substituted group.

Examples of the halogen atom represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably fluorine atom or chlorine atom.

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a methyl group It is preferable, and it is more preferable that it is a hydrogen atom.

The hydrogen atom contained in the amino group represented by R ^21A and R ^22A may be substituted with an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group containing an acryloyl group or a methacryloyl group. .

The aryl group which may have a substituent WHEREIN: As an aryl group, a C6-C14 aryl group, such as a phenyl group, a naphthyl group, and anthracenyl group, is mentioned, As the substituent which the said aryl group may have, a halogen atom and a C1-C8 group of an alkyl group.

In the alkyl group which may have a substituent, as an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2 -Ethylhexyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, Cyclooctyl group, cyclononyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1-(adamantan-1-yl)alkan-1-yl group, nor A C1-C20 alkyl group, such as a bornyl group, a methyl norbornyl group, and an isobornyl group, is mentioned. -CH ₂ - other than -CH ₂ - adjacent to the nitrogen atom contained in the alkyl group may be substituted with -O-, and examples of the substituent which the alkyl group may have include an amino group, a substituted amino group, a halogen atom and a silicon atom. and a group comprising

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the substituted amino group include methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, sec-butylamino group, tert-butylamino group, dimethylamino group, diethylamino group, dipropylamino group, ethylmethylamino group, etc. having 1 to 8 carbon atoms. an alkylamino group and a dialkylamino group having 1 to 8 carbon atoms.

The group containing an acryloyl group or a methacryloyl group means a group having at least one acryloyl group or a methacryloyl group as a structural unit of the group.

Carbon number of group containing an acryloyl group or a methacryloyl group is 3-30 normally, Preferably it is 3-20.

It is preferable that the group containing an acryloyl group or a methacryloyl group is group containing an acryloyloxy group or a methacryloyloxy group.

It is preferable that the group containing an acryloyl group or a methacryloyl group is group represented by Formula (A7-1).

[In formula ( ^A7-1 ), R 15A represents an acryloyl group or a methacryloyl group. R ^14A represents an alkanediyl group having 1 to 8 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -O-. * indicates a bond with a nitrogen atom.]

Examples of the alkanediyl group having 1 to 8 carbon atoms represented by R ^14A include a methylene group, an ethylene 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, heptane-1,7-diyl group, octane-1,8-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-1,2-di Diyl, propane-2,2-diyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4- A diyl group and 2-methylbutane-1,4-diyl group are mentioned, Preferably it is a C1-C4 alkanediyl group, More preferably, it is a methylene group or an ethylene group, More preferably, it is a methylene group. .

Examples of the group containing an acryloyl group or a methacryloyl group include the groups described below. (* indicates a bond with a nitrogen atom.)

Examples of the optionally substituted amino group represented by R ^21A and R ^22A include a methylamino group, an ethylamino group, a propylamino group, an isopropylamino group, a butylamino group, an isobutylamino group, a sec-butylamino group, a tert-butylamino group, a pentylamino group, and a neopentyl group. Amino group, hexylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, ethylmethylamino group, ethylisopropylamino group, ethylpropylamino group, isopropylmethylamino group, isopropylpropylamino group, methylpropylamino group, phenylamino group , naphthylamino group, 2-methylphenylamino group, 4-methylphenylamino group, 3-methylphenylamino group, 3,5-dimethylphenylamino group, 4-ethylphenylamino group, N-methyl-N-phenylamino group, acryloyloxymethylamino group, N-(acryloyloxymethyl)-N-methylamino group, N-(acryloyloxyethyl)-N-ethylamino group, N-(methacryloyloxyethyl)-N-ethylamino group, N-(acryl Royloxyethyl)-N-phenylamino group, N-(acryloyloxyethyl)-N-(methacryloyloxymethyl)amino group, N-(acryloyloxyethyloxymethyl)-N-ethylamino group, and N-(methacryloyloxyethyloxymethyl)-N-ethylamino group is mentioned.

The heteroaromatic hydrocarbon group represented by D may have at least one hetero atom, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

The heteroaromatic hydrocarbon group represented by D may be monocyclic or polycyclic.

Examples of the heteroaromatic hydrocarbon group represented by D include a pyridyl group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, and a benzoisothiazolyl group. and heteroaromatic hydrocarbon groups having 2 to 8 carbon atoms such as , thienyl group and benzothienyl group, and a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms including at least one nitrogen atom or sulfur atom as a component of the ring is preferable.

Examples of the substituent which the heteroaromatic hydrocarbon group represented by D may have include an amino group which may be substituted, an alkyl group having 1 to 20 carbon atoms, and an aryl group which may have a substituent, and an amino group which may be substituted and aryl which may have a substituent group is preferred.

As an amino group which may be substituted, the thing similar to the amino group which may be substituted represented by R ^21A and R ^22A is mentioned.

Examples of the alkyl group having 1 to 20 carbon atoms include the same groups as the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A .

A phenyl group, a naphthyl group, and an anthracenyl group are mentioned as an aryl group which may have a substituent, As a substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; and an alkyl group having 1 to 20 carbon atoms.

It is preferable that the heteroaromatic hydrocarbon group represented by D is group represented by Formula (III).

[In formula (III), X represents an oxygen atom or a sulfur atom.

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may have a substituent.

R ⁵⁶ represents an optionally substituted amino group.

* indicates a bond with a carbon atom.]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ include the same alkyl groups having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A . there is.

Examples of the aryl group which may have a substituent represented by R ⁵⁵ include a phenyl group.

Examples of the optionally substituted amino group represented by R ⁵⁶ include the same groups as the optionally substituted amino group represented by R ^21A and R ^22A .

R ⁵⁵ is preferably an unsubstituted or substituted aryl group, and more preferably an unsubstituted or halogen atom-substituted aryl group.

R ⁵⁶ is preferably an optionally substituted amino group.

Examples of the heteroaromatic hydrocarbon group represented by D include a group represented by formula (III-1) to a group represented by formula (III-8), and preferably a group represented by formula (III-1) or (III-2). ) is a group represented by

g is an arbitrary natural number, Preferably it is a natural number of 1-2, More preferably, it is 1.

G ^{g -} represents a g-valent anion, and is not limited as long as a salt is formed with a cation and a g-valent anion. For example, when g is a natural number of 2 or more, it may have one g-valent anion, and may have monovalent|monohydric anion or monovalent|monohydric anion site|parts g.

G ^{g −} is preferably a monovalent anion, for example, halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion, anion represented by formula (y1), formula (y2) ) and an anion represented by formula (y3).

[In the formula (y1), R ^B1 represents a hydrocarbon group which may have a halogen atom.

In the formula (y2), R ^B2 and R ^B3 each independently represent a halogen atom or a halogenated hydrocarbon group, or R ^B2 and R ^B3 are bonded to each other to include -SO ₂ -N ^- -SO ₂ - form a ring

In the formula (y3), M represents an aluminum atom or a boron atom, and R ^B4 and R ^B5 each independently represent a phenyl group which may have a substituent.]

Examples of the hydrocarbon group represented by R ^B1 include an alkyl group having 1 to 8 carbon atoms and an aromatic hydrocarbon group having 6 to 14 carbon atoms.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, 2-ethylhexyl group , an octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group.

A phenyl group and a naphthyl group are mentioned as a C6-C14 aromatic hydrocarbon group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

Examples of the halogenated alkyl group having 1 to 8 carbon atoms include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, perfluoro Roethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl)- 1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group , 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, dibromomethyl group, and tribromomethyl group, preferably having 1 to 8 carbon atoms is a fluorinated alkyl group of

Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples thereof include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a difluorophenyl group, a 1-fluoro-4-chlorophenyl group, a trifluorophenyl group, and a fluoronaphthyl group.

It is preferable that it is a C1-C8 halogenated alkyl group, and, as for R ^B1 , it is more preferable that it is a C1-C8 fluorinated alkyl group.

Examples of the halogen atom represented by R ^B2 and R ^B3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a fluorine atom or a chlorine atom.

Examples of the halogenated hydrocarbon group represented by R ^B2 and R ^B3 include a halogenated alkyl group having 1 to 8 carbon atoms and an aromatic hydrocarbon group having 6 to 14 carbon atoms having a halogen atom.

Examples of the halogenated alkyl group having 1 to 8 carbon atoms include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, perfluoro Roethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl)- 1,2,2,2-tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group , 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, dibromomethyl group, and tribromomethyl group, preferably having 1 to 8 carbon atoms is a fluorinated alkyl group of

Examples of the aromatic hydrocarbon group having a halogen atom having 6 to 14 carbon atoms include a phenyl group having a halogen atom and a naphthyl group having a halogen atom. Specific examples thereof include a fluorophenyl group, a chlorophenyl group, a bromophenyl group, a difluorophenyl group, a 1-fluoro-4-chlorophenyl group, a trifluorophenyl group, and a fluoronaphthyl group.

It is preferable that R ^B2 and R ^B3 are the same group.

R ^B2 and R ^B3 are each independently preferably a fluorinated alkyl group having 1 to 8 carbon atoms, more preferably a trifluoromethyl group.

As a substituent which the phenyl group represented by R ^B4 and R ^B5 may have, a hydroxyl group is preferable.

It is preferable that R ^B4 and R ^B5 are the same group.

Examples of the anion represented by the formula (y1) include methanesulfonic acid anion, toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion, trifluoromethanesulfonic acid anion, perfluorobutanesulfonic acid anion, phenylsulfonic acid anion, and fluoro A rophenylsulfonic acid anion etc. are mentioned.

Examples of the anion represented by the formula (y2) include the anions described below.

Examples of the anion represented by the formula (y3) include the anions described below.

Examples of the dye (A7) include compounds represented by formulas (A-I-a1) to (A-I-a15). The compound represented by the formula (A-I-a5) to the compound represented by the formula (A-I-a12) are preferable.

The dye (A7) can be manufactured, for example, by the method described in Korean Patent Application Laid-Open No. 2014-0026284.

A monomer may be sufficient as blue or purple dye, and a polymer may be sufficient as it. The blue or purple dye polymer is a polymer containing a structural unit derived from a blue or purple dye, and may be a polymer consisting only of a structural unit derived from a blue or purple dye, or may have a structure different from the structural unit derived from the blue or purple dye. A copolymer containing a unit (hereinafter, sometimes referred to as copolymer (a)) may be used. The structural unit derived from the blue or purple dye may be a divalent or higher valence group generated by polymerization of a polymerizable blue or purple dye, or a monovalent or higher valent group formed by removing one or more hydrogen atoms from the blue or purple dye. As the copolymer (a), in addition to the structural unit derived from a blue or purple dye, a structural unit derived from a monomer having an ethylenically unsaturated bond, and a structural unit represented by the formulas (1) to (3) described below. and a copolymer comprising at least one selected from

Moreover, the copolymer (a) may be a copolymer containing the structural unit derived from the monomer which guide|induced the resin (B) mentioned later, and the structural unit guide|guided|derived from blue or purple dye.

[In formula (1), R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and even if they have a substituent represents an alkylaryl group or a combination thereof.

m' represents an integer of 0-5.]

[In formula (2), R ¹¹ is a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, optionally substituted alkylaryl group, or these represents a combination.

R ¹² represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, -CO-R ¹⁷ -COOH, or a combination thereof.

R 17 represents an optionally substituted alkylene group having 1 to 30 carbon atoms or an optionally substituted ^alkoxyylene group having 1 to 30 carbon atoms.]

[In formula (3), R ¹³ and R ¹⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, and even if they have a substituent represents an alkylaryl group or a combination thereof.

R ¹⁵ represents -COOH or -CONHR ¹⁸ .

R ¹⁸ represents an optionally substituted alkyl group having 1 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms.

R ¹⁶ represents -COOH, and R ¹⁵ and R ¹⁶ are bonded to each other to form a ring.]

The monomer having an ethylenically unsaturated bond is an ethylenically unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid.

The weight ratio of the monomer having an ethylenically unsaturated bond is usually 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to the total weight of the monomers forming the copolymer (a). -30% by weight.

Moreover, it may contain the structural unit derived from the monomer which has an ethylenically unsaturated bond, and the structural unit derived from the monomer copolymerizable, specifically,

alkenyl aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, and vinylbenzylmethyl ether;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxybutyl acrylic unsaturated carboxylic acid ester compounds such as lactate, 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, and phenyl methacrylate;

unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate and 2-dimethylaminoethyl methacrylate;

vinyl carboxylate ester compounds such as vinyl acetate and vinyl benzoate;

unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate;

vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;

Unsaturated amide compounds, such as acrylamide and methacrylamide, and these combinations are mentioned.

The structural unit derived from the blue or purple dye contained in the copolymer (a) is selected from the group consisting of a structural unit derived from a triarylmethane dye (A4) and a structural unit derived from a dye represented by formula (A7) It is preferable that it is at least 1 type used.

As the structural unit derived from the triarylmethane dye (A4), each structural unit derived from the compound represented by the formula (2b-1) to the compound represented by the formula (2b-13) described above is preferable.

As the structural unit derived from the dye represented by the formula (A7), a structural unit derived from the compound represented by the formula (A-I-a15) described above is preferable.

The content of the dye (A2) is C.I. With respect to 100 mass parts of acid red 52, it is 80-10000 mass parts normally, Preferably it is 80-7500 mass parts, More preferably, it is 80-1000 mass parts, More preferably, it is 80-600 mass parts.

<Dye (Ac) and Pigment (Ad)>

It does not specifically limit as dye (Ac), A well-known dye can be used.

It does not specifically limit as a pigment (Ad), A well-known pigment can be used, For example, the pigment classified as a pigment by the color index (The Society of Dyers and Colorists publication) is mentioned.

As a pigment, C.I. Purple pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc. are mentioned.

It is preferable that the coloring agent (A) is a coloring agent containing the combination described below.

(1) blue pigment (A1), C.I. Acid Red 52 and Blue or Purple Dyes (A2)

(2) blue pigment (A1), C.I. Acid Red 52, blue or purple dye (A2) and violet pigment (Ad)

To [ content of a coloring agent (A) ] with respect to the total amount of solid content, Preferably it is 5-60 mass %, More preferably, it is 8-55 mass %, More preferably, it is 10-50 mass %. When the content of the colorant (A) is within the above range, the color density when a color filter is used is sufficient, and the resin (B) and the polymerizable compound (C) can be contained in the required amount in the composition, so a pattern with sufficient mechanical strength can form. Here, the "total amount of solid content" in this specification means the quantity remove|excluding content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1] at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, and ethylene a copolymer of a monomer (b) having a sexually unsaturated bond (hereinafter sometimes referred to as “(b)”);

Resin [K2] (a) and (b) and (a) and copolymerizable monomer (c) (however, different from (a) and (b)) (hereinafter referred to as “(c)” in some cases) of copolymers;

resin [K3] copolymer of (a) and (c);

Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);

Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);

Resin [K6] (a) is reacted with the copolymer of (b) and (c), and further, carboxylic acid anhydride

A resin that has been reacted with water.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

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, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hepto-2-ene, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene , 5-Carboxy-5-methylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hepto-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride;

Unsaturated mono[(meth)acryloyloxyalkyl] of polyhydric carboxylic acids with more than divalence, such as mono[2-(meth)acryloyloxyethyl succinate] and mono[2-(meth)acryloyloxyethyl phthalate] esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility point with respect to the aqueous alkali solution of resin obtained.

(b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond It refers to a polymerizable compound having (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

As (b), for example, a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”); and the like.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-1)”), an alicyclic unsaturated hydrocarbon and a monomer (b1-2) having a structure in which hydrocarbons are epoxidized (hereinafter sometimes referred to as “(b1-2)”).

As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl benzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene; 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. are mentioned. can

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Seroxide 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl (meta). ) acrylate (eg, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer M100; manufactured by Daicel Corporation), formula ( The compound represented by the compound represented by I), the compound represented by Formula (II), etc. are mentioned.

[In Formulas (1) and (II), R ^a and R ^b represent 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 ^a and X ^b represent a single bond, -R ^c -, *-R ^c -0-, *-R ^c -S-, or *-R ^c -NH-.

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

* indicates a bond with O.]

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

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

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably 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 group. ,6-diyl group, etc. are mentioned.

As X ^a and X ^b , Preferably, a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O- are mentioned, More preferably, a single bond, *- CH ₂ CH ₂ -O- is mentioned (* represents a bond with O).

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1) - Formula (I-15) are mentioned. Preferably formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) The compound represented by ) is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9), or Formula (I-15) is mentioned.

As a compound represented by Formula (II), the compound etc. which are represented by Formula (II-1) - Formula (II-15) are mentioned. Preferably, a formula (II-1), a formula (II-3), a formula (II-5), a formula (II-7), a formula (II-9), or a formula (II-11) - a formula (II-15) The compound represented by ) is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

The compound represented by Formula (1) and the compound represented by Formula (II) can be used independently, respectively, respectively. Moreover, they can be mixed in arbitrary ratios. When mixing, the mixing ratio is in a molar ratio, preferably in the formula (I):formula (II), 5:95 to 95:5, more preferably 10:90 to 90:10, still more preferably 20 :80 to 80:20.

As (b2), the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As (b), it is preferable that it is (b1) at the point which can further make reliability, such as heat resistance and chemical-resistance of the color filter obtained high. Moreover, the point which is excellent in the storage stability of colored curable resin composition to (b1-2) is more preferable.

As (c), for example, 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, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, as a common name as "dicyclopentanyl (meth) acrylate" Also, it is sometimes referred to as "tricyclodecyl (meth)acrylate."), tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate (in the art, Commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylic acid esters such as (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

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

Bicyclo[2.2.1]hepto-2-ene, 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxybi Cyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2 -ene, 5-methoxybicyclo[2.2.1]hepto-2-ene, 5-ethoxybicyclo[2.2.1]hepto-2-ene, 5,6-dihydroxybicyclo[2.2.1]hepto -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto- 2-ene, 5,6-dimethoxybicyclo[2.2.1]hepto-2-ene, 5,6-diethoxybicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-methyl Bicyclo[2.2.1]hepto-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-2-ene, 5-phenoxy Cycarbonylbicyclo[2.2.1]hepto-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hepto-2-ene, 5,6-bis(cyclohexylox bicyclo unsaturated compounds such as cycarbonyl)bicyclo[2.2.1]hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutylate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, styrene, vinyltoluene, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] hepto-2-ene, etc. are preferable from the point of copolymerization reactivity and heat resistance. Do.

In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1],

the structural unit derived from (a); 2-60 mol%

the structural unit derived from (b); 40-98 mol%

It is preferable that

the structural unit derived from (a); 10-50 mol%

the structural unit derived from (b); 50-90 mol%

It is more preferable that

When the ratio of the structural unit of resin [K1] exists in said range, there exists a tendency excellent in the storage stability of a colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the color filter obtained.

Resin [K1] is, for example, the method described in the document "Experimental method of polymer synthesis" (published by Takayuki Otsu, Chemical Dongin, 1st edition, 1st edition, March 1, 1972) and the method described in this document It can be prepared with reference to the cited literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are put in a reaction vessel, for example, by replacing oxygen with nitrogen, a deoxidized atmosphere is created, and heating and keeping warm while stirring how to do it In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, What is normally used in the said field|area can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) ) is mentioned, what is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored curable resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, so the colored curable resin of the present invention The manufacturing process of the composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2],

the structural unit derived from (a); 2-45 mol%

the structural unit derived from (b); 2-95 mol%

the structural unit derived from (c); 1-65 mol%

It is preferable that

the structural unit derived from (a); 5-40 mol%

the structural unit derived from (b); 5-80 mol%

the structural unit derived from (c); 5-60 mol%

It is more preferable that

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent tends to

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

In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3],

the structural unit derived from (a); 2-60 mol%

the structural unit derived from (c); 40-98 mol%

It is preferable that

the structural unit derived from (a); 10-50 mol%

the structural unit derived from (c); 50-90 mol%

It is more preferable that

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

Resin [K4] is produced by obtaining the copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and/or carboxylic acid anhydride of (a). can do.

First, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as that quoted in resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the said copolymer.

Continuing with the preparation of the copolymers of (a) and (c), the atmosphere in the flask is substituted from nitrogen to air, and (b), a reaction catalyst of carboxylic acid or carboxylic acid anhydride and a cyclic ether (e.g., Tris (dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask, and the resin [K4] is prepared by, for example, reacting at 60 to 130° C. for 1 to 10 hours. can

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the balance of the storage stability of colored curable resin composition, the developability at the time of forming a pattern, and solvent resistance, heat resistance, mechanical strength, and a sensitivity of the pattern obtained to become favorable. Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K4], (b1) is preferable and (b1-1) is more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c).

Reaction conditions, such as an introduction method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the introduction method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

Resin [K5] is a 1st step, it carries out similarly to the manufacturing method of resin [K1] mentioned above, and obtains the copolymer of (b) and (c). Similarly to the above, the obtained copolymer may use the solution after reaction as it is, may use a concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all structural units constituting the copolymer,

the structural unit derived from (b); 5-95 mol%

the structural unit derived from (c); 5-95 mol%

It is preferable that

the structural unit derived from (b); 10-90 mol%

the structural unit derived from (c); 10-90 mol%

It is more preferable that

Further, under the same conditions as in the production method of the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is reacted with the carboxylic acid or carboxylic acid anhydride of (a). By doing this, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K5], (b1) is preferable and (b1-1) is more preferable.

Resin [K6] is resin in which carboxylic acid anhydride was further made to react with resin [K5]. A hydroxy group generated by the reaction of a cyclic ether with carboxylic acid or carboxylic acid anhydride is reacted with carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride (hymic acid anhydride), etc. are mentioned. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth) resins such as acrylic acid copolymer [K1]; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6 ]Resins such as decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; resins [K3] such as benzyl (meth)acrylate/(meth)acrylic acid copolymer and styrene/(meth)acrylic acid copolymer; Resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) to tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer ) Resin to which acrylate was added, resin [K4], such as a resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; Tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymer with (meth)acrylic acid, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer; and resin [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride. there is.

Among these, as resin (B), resin [K1] and resin [K2] are preferable.

The weight average molecular weight of resin (B) in terms of polystyrene becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, the solubility in the developer of the unexposed part is good, and the resolution of the colored pattern tends to be improved.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) becomes like this. Preferably it is 50-170 mg-KOH/g, More preferably, it is 60-150, More preferably, it is 70-135 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ content of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, etc., preferably Preferably, it is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Erythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (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, etc. are mentioned.

Among these, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, it is 250-1,500 or less.

It is preferable that content of a polymeric compound (C) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When content of a polymeric compound (C) exists in the said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating an active radical, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used.

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

As the O-acyloxime compound, for example, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) ) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-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-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2) -Methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. You may use commercial items, such as Irgacure OXEO1, OXEO2 (above, BASF company make), and N-1919 (made by ADEKA company). The O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1 At least one selected from the group consisting of -one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferable, and N- More preferred is benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine. If it is these O-acyl oxime compounds, there exists a tendency for the color filter of high brightness to be obtained.

The alkylphenone compound is 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2- Benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, 2-hydroxy- 2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl and ketones, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyldimethyl ketal. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

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) To methyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) tenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine etc. are mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl) -4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2, 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (For example, see Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) .), an imidazole compound in which the phenyl group at the 4,4'5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Moreover, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (especially amines) mentioned later.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfo Nate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, di Onium salts, such as phenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in the said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

<Polymerization initiation aid (D1)>

A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

As polymerization initiation adjuvant (D1), an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylaminobenzoic acid. 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4' -bis(ethylmethylamino)benzophenone etc. are mentioned, Among these, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibu Toxanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy Oxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenyl Sulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

When using polymerization initiation adjuvant (D1), the content becomes like this with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. is the mass part. When the amount of the polymerization initiation adjuvant (D1) is within this range, a coloring pattern can be formed more highly sensitively, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -0-), ether solvents (solvents containing -0- in the molecule and not containing -COO-), ether esters Solvents (solvents containing -COO- and -0- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

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

As the ether solvent, 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and methylanisole 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, and methyl 3-ethoxypropionate. , 3-ethoxypropionate ethyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono and propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo pentanone, cyclohexanone, isophorone, and the like.

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

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

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

Among the above solvents, organic solvents having a boiling point of 120°C or more and 180°C or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. As a solvent, Propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy -4-methyl-2-pentanone and N,N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

To [ content of a solvent (E) ] the total amount of the colored curable resin composition of this invention, Preferably it is 70-95 mass %, More preferably, it is 75-92 mass %. In other words, the total amount of solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in the said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Leveling agent (F)>

As a leveling agent (F), silicone type surfactant, the silicone type surfactant etc. which have a silicone type surfactant, a fluorine type surfactant, and a fluorine atom are mentioned. These may have a polymerizable group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicon DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan joint venture), etc. can be heard

As said fluorochemical surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, copper FC431 (manufactured by Sumitomo Re-M Co., Ltd.), Megapack (registered trademark) F142D, Dong F171, Dong F172, Dong F173, Dong F177, Dong F183, Dong F554, Copper R30, Copper RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, Copper EF303, Copper EF351, Copper EF352 (Mitsubishi Material Electronics Co., Ltd.), Sufflon (registered trademark) ) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapack (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

With respect to the total amount of colored curable resin composition, content of a leveling agent (F) becomes like this. Preferably they are 0.001 mass % or more and 0.2 mass % or less, Preferably they are 0.002 mass % or more and 0.1 mass % or less, More preferably, they are 0.01 mass %. or more and 0.05 mass% or less. When content of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other high molecular compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

<Method for producing colored curable resin composition>

The colored curable resin composition of the present invention is, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E), a leveling agent ( It can prepare by mixing F), polymerization initiation adjuvant (D1), and other components.

The dye (A2) and the dye (Ac) used as needed may be previously dissolved in one part or all of a solvent (E), respectively, and a solution may be prepared. It is preferable to filter the said solution with a filter with a pore diameter of about 0.01-1 micrometer.

It is preferable to mix a blue pigment (A1) with a part or all of a solvent (E) beforehand, and to disperse|distribute it using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix|blend a part or all of the said pigment dispersant and resin (B) as needed. The target colored curable resin composition can be prepared by mixing the remaining component with the pigment dispersion liquid obtained in this way so that it may become predetermined density|concentration.

It is preferable to filter the colored curable resin composition after mixing with a filter with a hole diameter of about 0.01-10 micrometers.

According to the colored curable resin composition of this invention, especially the color filter excellent in heat resistance can be manufactured. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

[Example]

Hereinafter, the colored curable resin composition of this invention is demonstrated in more detail by an Example. In the examples, "%" and "parts" are mass % and parts by mass, unless otherwise specified.

In the following synthesis examples, compounds were identified by mass spectrometry (LC; Agilent type 1200, MASS; Agilent product LC/MSD type) or elemental analysis (VARIO-EL; (Elemental Co., Ltd.)).

[Synthesis Example 1]

20 parts of the compound represented by Formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was stirred at 110°C for 6 hours. The resulting reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain 24 parts of a compound represented by the formula (1-24) (hereinafter referred to as "xanthene dye 1"). The yield was 80%.

Identification of a compound represented by formula (1-24);

(mass spectrometry) ionization mode=ESI+: m/z=[M+H] ⁺ 603.4

Exact Mass: 602.2

[Synthesis Example 2]

15 parts of a mixture of the compound represented by the formula (A0-1) and the compound represented by the formula (A0-2) (trade name Chugai Aminol Fast Pink R; medium-extensible agent) in a flask equipped with a cooling tube and a stirring device; 150 parts of chloroform and 8.9 parts of N,N-dimethylformamide were charged, and 10.9 parts of thionyl chloride were added dropwise while maintaining 20°C or lower under stirring. After completion of the dropwise addition, the temperature was raised to 50°C, maintained at the same temperature for 5 hours to react, and then cooled to 20°C. The mixture solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was dripped and added to the reaction solution after cooling, maintaining at 20 degrees C or less under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Then, after solvent distillation of the obtained reaction mixture with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added while stirring in the liquid mixture of 375 parts of ion-exchange water, and the crystal|crystallization was precipitated. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60°C to obtain a compound represented by xanthene dye 2 (formula (Aa-1-1) to (Aa-1-8)). mixture) of 11.3 parts.

[Synthesis Example 3]

The following reaction was performed in nitrogen atmosphere. After putting 36.3 parts of potassium thiocyanate and 160.0 parts of acetone into the flask provided with the cooling tube and a stirring apparatus, it stirred at room temperature for 30 minutes. Next, 50.0 parts of benzoic acid chloride (made by Tokyo Chemical Industry Co., Ltd.) was dripped over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after cooling the reaction mixture on ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, after cooling the reaction mixture on ice, 34.2 parts of 30% aqueous sodium hydroxide solution were added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Then, 35.3 parts of chloroacetic acid were dripped at room temperature. After completion of the dropwise addition, the mixture was stirred under heating and reflux for 7 hours. Then, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. Then, stirring was stopped, and when it left still for 30 minutes, it wasolate|separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated brine. After adding an appropriate amount of dandelion vinegar to the organic layer and stirring for 30 minutes, filtration was performed to obtain a dried organic layer. The obtained organic layer was solvent-distilled with an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60°C under reduced pressure to obtain 52.0 parts of the compound represented by the formula (B-I-1). Yield 50%

The following reaction was performed in nitrogen atmosphere. To a flask equipped with a cooling tube and a stirring device, 9.3 parts of the compound represented by the formula (BI-1), 10.0 parts of 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.), and 20.0 parts of toluene After adding 14.8 parts of phosphorus oxychloride, 14.8 parts of phosphorus oxychloride was then added, and it stirred at 95-100 degreeC for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170.0 parts of isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added, followed by stirring for 30 minutes. Then, stirring was stopped, and when it left still for 30 minutes, it wasolate|separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of dandelion root was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was solvent-distilled by the evaporator, and the blue-violet solid was obtained. Furthermore, the blue-violet solid was dried at 60 degreeC under reduced pressure, and 19.8 parts of compounds represented by Formula (A-I-a1) were obtained. Yield 100%

Identification of the compound represented by the formula (A-I-a1)

(mass spectrometry) ionization mode = ESI+: m/z=601.3 [M-Cl] ⁺

Exact Mass: 636.3

The following reaction was performed in nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of the compound represented by the formula (AI-a1), 4.5 parts of bis(trifluoromethanesulfonyl)imilithium (manufactured by Tokyo Chemical Industry Co., Ltd.), and N; After adding 100.0 parts of N-dimethylformamide, it stirred at 50-60 degreeC for 3 hours. Then, after cooling the reaction mixture to room temperature, it was dripped at 2000.0 parts of tap water with stirring for 1 hour, dark blue suspension was obtained. When the resulting suspension was filtered, a blue-green solid was obtained. Furthermore, the cyan solid was dried at 60 degreeC under reduced pressure, and 11.3 parts of compounds represented by Formula (A-I-a9) were obtained. Yield 82%

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, 305 parts by mass of ethyl lactate was put, and the mixture was heated to 70°C while stirring. Next, 46 parts by mass of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1) are mixed in a molar ratio; Mix at 50:50.) 240 parts by mass were dissolved in 185 parts by mass of ethyl lactate to prepare a solution, and the solution was added dropwise to a flask kept at 70°C over 4 hours using a dropping funnel.

On the other hand, a solution obtained by dissolving 30 parts by mass of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, it was maintained at 70° C. for 4 hours, and then cooled to room temperature, the weight average molecular weight Mw was 9.1×10 ³ , molecular weight distribution was 2.1, solid content 26 mass%, solid content acid value A 120 mg-KOH/g resin B1 solution was obtained. Resin B1 has a structural unit shown below.

[Synthesis Example 5]

Into a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel and a nitrogen introduction tube, 182 parts of propylene glycol monomethyl ether acetate was introduced, the atmosphere in the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 2,2'- to a mixture consisting of 70.5 parts of acrylate, 43.0 parts of methacrylic acid, 22.0 parts of tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 parts of propylene glycol monomethyl ether acetate The solution to which 3.6 parts of azobisisobutyronitrile was added was dripped, and stirring was continued at 100 degreeC.

Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110°C to obtain a resin B2 solution having a solid content of 29% and a solid content acid value of 79 mgKOH/g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

column temperature; 40℃

menstruum; THF (tetrahydrofuran)

flow rate; 1.OmL/min

detector; RI

calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Toso Corporation)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution.

[Synthesis Example 6]

To 28.52 parts of bisN-ethyl-N-hydroxyethylaminobenzophenone and 17.80 parts of triethylamine, 50 mL of dichloromethane was added and dissolved with stirring. Then, 13.56 parts of methacrylic acid anhydride was added, and it heated up and maintained at 40 degreeC. After completion of the reaction, after cooling to room temperature, water was added to separate the layers, and 20 mL of a saturated sodium chloride solution was added, followed by stirring for 30 minutes. After the layer separation, the organic layer was distilled off, and the remaining solid was dried under reduced pressure to obtain 21.4 parts of the compound represented by the formula (aa2).

21.4 parts of the compound represented by Formula (aa2) was added to 500 mL of chloroform, and it stirred. Then, 49.08 parts of phosphorus oxychloride was added, and it stirred for 15 minutes. After adding 14.56 parts of N-phenyl-1-naphthylamine, it was refluxed. After completion of the reaction, after cooling to room temperature, water was added and stirred. After stirring, it was allowed to stand, and the layers were separated, the organic layer was distilled off, and the remaining solid was dried under reduced pressure and purified to obtain 20.3 parts of the compound represented by the formula (aa3).

[Synthesis Example 7]

10.00 parts of the compound represented by the formula (aa3) was added to 100 mL of methanol for dissolution, and then 2.50 parts of sodium trifluoromethanesulfonate was added to replace the salt. After filtration, the obtained compound was washed with water, and the remaining solid was dried under reduced pressure to obtain 5.5 parts of the compound represented by the formula (aa4).

[Synthesis Example 8]

After adding 10.00 parts of the compound represented by Formula (aa3) to 100 mL of methanol and dissolving, 2.09 parts of lithium bistrifluoromethanesulfonimides were added and the salt was substituted. After filtration, the obtained compound was washed with water and dried under reduced pressure to obtain 7.5 parts of the compound represented by the formula (aa5).

[Synthesis Example 9]

In nitrogen atmosphere, after putting 30 parts of methyl ethyl ketone, it heated up at 70 degreeC. 2.54 parts of the compound represented by the formula (aa4), 0.16 parts of 2,2'-azobisisobutyronitrile, and 20 parts of methyl ethyl ketone were dissolved, and the mixture was added to the reactor while maintaining 70° C. for 3 hours. After completion of the input, the temperature was maintained at 70° C. for 8 hours, methyl ethyl ketone was partially concentrated, the reaction solution was added to hexane, crystals were precipitated, filtered, and the remaining solid was washed with hexane and dried under reduced pressure. 1.80 parts of a polymer compound (aa4) was obtained.

[Synthesis Example 10]

In nitrogen atmosphere, after putting 30 parts of methyl ethyl ketone, it heated up at 70 degreeC. 2.54 parts of the compound represented by the formula (aa4), 0.25 parts of 2,2'-azobisisobutyronitrile, 0.51 parts of benzyl methacrylate, 0.51 parts of methacrylic acid, 0.42 parts of N-phenylmaleimide in 50 parts of methyl ethyl ketone It was dissolved and put in the reactor at 70° C. for 3 hours. After completion of the input, the temperature was maintained at 70° C. for 8 hours, methyl ethyl ketone was partially concentrated, the reaction solution was added to hexane, crystals were precipitated, filtered, and the remaining solid was washed with hexane and dried under reduced pressure. 2.35 parts of a polymer compound (aa4') was obtained.

[Synthesis Example 11]

In nitrogen atmosphere, after putting 30 parts of methyl ethyl ketone, it heated up at 70 degreeC. 2.54 parts of the compound represented by the formula (aa5), 0.16 parts of 2,2'-azobisisobutyronitrile, and 20 parts of methyl ethyl ketone were dissolved, and the mixture was added to the reactor while maintaining 70° C. for 3 hours. After completion of the input, the temperature was maintained at 70° C. for 8 hours, methyl ethyl ketone was partially concentrated, the reaction solution was added to hexane, crystals were precipitated, filtered, and the remaining solid was washed with hexane and dried under reduced pressure. 1.63 parts of a polymer compound (aa5) was obtained.

[Synthesis Example 12]

In a nitrogen atmosphere, after putting 30 parts of methyl ethyl ketone, it heats up to 70 degreeC. 2.54 parts of the compound represented by the formula (aa5), 0.25 parts of 2,2'-azobisisobutyronitrile, 0.51 parts of benzyl methacrylate, 0.51 parts of methacrylic acid, 0.42 parts of N-phenylmaleimide in 50 parts of methyl ethyl ketone After dissolving, the reactor is kept at 70°C and put in for 3 hours. After completion of the input, the temperature was maintained at 70° C. for 15 hours, methyl ethyl ketone was partially concentrated, the reaction solution was added to hexane, crystals were precipitated, filtered, and the remaining solid was dried under reduced pressure to dry the polymer compound (aa5'). ) get 3.80 copies.

[Synthesis Example 13]

After adding 5.00 parts of the compound represented by Formula (aa3) to 50 mL of methanol and dissolving, 1.46 parts of p-toluenesulfonic acid sodium salt is added and the salt is substituted. After filtration, the obtained compound is washed with water and dried under reduced pressure to obtain 2.84 parts of the compound represented by the formula (aa6).

[Synthesis Example 14]

C.I. After dissolving 5.00 parts of Basic Blue 26 by adding 50 mL of methanol, 2.10 parts of p-toluenesulfonic acid sodium salt is added to replace the salt. After filtration, the obtained compound is washed with water and dried under reduced pressure to obtain 2.71 parts of the compound represented by the formula (aa7).

[Synthesis Example 15-18]

In a flask equipped with a cooling tube and a stirrer, a monomer represented by the formula (aa5) (hereinafter sometimes referred to as dye Dy), benzyl methacrylate, methacrylic acid, methyl methacrylate and N-benzyl maleimide was added in the weight ratio shown in Table 1, and 6 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) (initiator) was added based on 100 parts by weight of the total amount of the monomer. Then, 300 parts by weight of propylene glycol monomethyl ether acetate was added with respect to 100 parts by weight of the total amount of the initiator and the monomer, and then stirring was gradually started under a nitrogen atmosphere. The reaction solution was heated up to 90°C and stirred for 10 hours to obtain a copolymer.

[Synthesis Example 19-22]

In a flask equipped with a cooling tube and a stirrer, the monomers represented by the formula (aa8), benzyl methacrylate, methacrylic acid, methyl methacrylate, and N-benzyl maleimide were added at the weights shown in Table 2 below, respectively, As an initiator, 2,2'-azobis(2,4-dimethylvaleronitrile is added in an amount of 6 parts by weight based on 100 parts by weight of the total amount of the monomer. Then, based on 100 parts by weight of the total amount of the initiator and the monomer, propylene glycol as a solvent After adding 300 parts by weight of monomethyl ether acetate (PGMEA), stirring is gradually started under a nitrogen atmosphere The reaction solution is heated to 90° C. and stirred for 10 hours to obtain a copolymer solution.

[Synthesis Example 23-26]

A copolymer solution was obtained in the same manner as in Synthesis Examples 19-22, respectively, except that the monomer represented by the formula (aa9) was used instead of the monomer represented by the formula (aa8).

[Synthesis Example 27-30]

A copolymer solution was obtained in the same manner as in Synthesis Examples 19-22, respectively, except that the monomer represented by the formula (aa10) was used instead of the monomer represented by the formula (aa8).

[Synthesis Example 31-42]

3.5% by weight of each copolymer solution prepared in Synthesis Examples 19-30, 12% by weight of blue pigment (BASF, B 15:6), 6% by weight of dispersant (BYK, Diperbyk 6919), and 78.5% by weight of propylene glycol monomethyl ether acetate % by weight is mixed and dispersed using a paint shaker for 24 hours to prepare respective copolymer dispersions 1 to 12.

[Synthesis Example 43]

Into the reactor, 25 parts of pararosaniline hydrochloride and 500 parts of ethanol are added, and the mixture is stirred at 200° C. for 8 hours. Then, the temperature of the solution is lowered to 25° C., and 174 parts of 2-methyl-2-propenoic-carboxyoxy ethyl ester is slowly added dropwise to the solution over 5 hours. Then, the temperature of the solution is raised to 70° C., followed by stirring for 24 hours. After completion of the reaction, it is slowly recrystallized from ethanol to obtain 54.5 parts of the compound represented by the formula (aa11).

[Synthesis Example 44]

Into the reactor, 25 parts of pararosaniline hydrochloride and 500 parts of ethanol are put, and the mixture is stirred at 200°C for 8 hours.

Then, the temperature is lowered to 25° C., and 209 parts of 2-methyl-2-propenoic-sulfamino ethyl ester is slowly added dropwise to the solution over 5 hours. Then, the temperature of the solution is raised to 70° C., followed by stirring for 24 hours.

After completion of the reaction, it is slowly recrystallized from ethanol to obtain 58.2 parts of the compound represented by the formula (aa12).

[Synthesis Example 45]

In Synthesis Example 6, except for using the compound represented by the formula (BI-1) instead of N-phenyl-1-naphthylamine, it was synthesized in the same manner as in Synthesis Example 6 to obtain a compound represented by the formula (aa13). .

[Synthesis Example 46-49]

A copolymer solution was obtained in the same manner as in Synthesis Examples 19-22, respectively, except that the monomer represented by the formula (aa13) was used instead of the monomer represented by the formula (aa8).

[Synthesis Example 50-53]

3.5% by weight of each copolymer solution prepared in Synthesis Examples 46-49, C.I. Pigment blue pigment 15:6 (BASF) 12% by weight, dispersant (BYK, Diperbyk 6919) 6% by weight, and propylene glycol monomethyl ether acetate 78.5% by weight were mixed, and dispersed using a paint shaker for 24 hours, Each copolymer dispersion 50-53 is prepared.

[Example 1]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): xanthene dye 1 2.2 parts

(A) Colorant: C.I. Acid Red 52 1.5 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 2]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): xanthene dye 2 1.3 parts

(A) Colorant: C.I. Acid Red 52 1.5 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 3]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A4): Basic Blue 7 1.3 parts

(A) Colorant: C.I. Acid Red 52 0.3 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 4]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

mixed, sufficiently dispersing the pigment using a bead mill, and then,

(A) Colorant (A5): 1.3 parts of a compound represented by the formula (2-29)

(A) Colorant: C.I. Acid Red 52 0.8 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 5]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate are mixed, the pigment is sufficiently dispersed using a bead mill, and then,

(A) Colorant (A6): 1.3 parts of a compound represented by the formula (3-11)

(A) Colorant: C.I. Acid Red 52 Part 1.1

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 6]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A7): 1.8 parts of a compound represented by the formula (A-I-a9)

(A) Colorant: C.I. Acid Red 52 0.3 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXEO1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Comparative Example 1]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) colorant (A3): xanthene dye 2 2.2 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Comparative Example 2]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) colorant (A3): xanthene dye 2 2.3 parts

(A) Colorant: C.I. Acid Red 52 3.0 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

<Production of Colored Patterns>

On a 5 cm corner glass substrate (Eagle 2000; manufactured by Corning), a colored curable resin composition was applied by a spin coating method, and then prebaked at 100°C for 3 minutes to obtain a colored layer. After cooling, the interval between the substrate on which the colored layer was formed and the quartz glass photomask was set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), in an atmospheric atmosphere, an exposure dose of 150 mJ/cm 2 (based on 365 nm) was irradiated with light. As a photomask, the thing in which the 100 micrometers line-and-space pattern was formed was used. The colored layer after light irradiation is immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, and after washing with water, post-baking at 200°C for 30 minutes in an oven was performed to obtain a coloring pattern.

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

<Chromaticity evaluation>

With respect to the obtained coloring pattern, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Co., Ltd.), and xy chromaticity coordinates (x, y) in the CIE XYZ color system using the characteristic function of the C light source. ) and tristimulus value Y were measured. It shows that the brightness is so high that the value of Y is large. A result is shown in Table 6.

[Heat resistance evaluation]

The coating film of the obtained colored curable resin composition was heated at 230 degreeC for 20 minutes, and the color difference (ΔEab*) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of performing the above heat resistance evaluation about the obtained coating film, the color difference (ΔEab*) is shown in Table 6. It shows that the color change before and behind a heating is small, and it is excellent in heat resistance, so that (triangle|delta)Eab* is small.

[Example 7]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the compound represented by Formula (aa4) obtained by the synthesis example 7, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 8]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the compound represented by Formula (aa5) obtained by the synthesis example 8, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 9]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the polymer compound (aa4) obtained by the synthesis example 9, it carries out similarly to Example 1, and obtains a colored curable resin composition.

[Example 10]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the polymer compound (aa4') obtained by the synthesis example 10, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 11]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the polymer compound (aa5) obtained by the synthesis example 11, it carries out similarly to Example 1, and obtains a colored curable resin composition.

[Example 12]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the polymer compound (aa5') obtained by the synthesis example 12, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 13]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the formula (aa6) obtained by the synthesis example 13, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 14]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the polymer compound (aa7) obtained by the synthesis example 14, it carries out similarly to Example 1, and obtains a colored curable resin composition.

[Example 15]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 2 parts

0.5 part of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.2 parts of the copolymer solution obtained in Synthesis Example 15

(A) Colorant: C.I. Acid Red 52 0.1 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXEO1; manufactured by BASF) 10 parts

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 16]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 2 parts

0.5 part of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.3 parts of the copolymer solution obtained in Synthesis Example 16

(A) Colorant: C.I. Acid Red 52 0.1 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 17]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 2 parts

0.5 part of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 17

(A) Colorant: C.I. Acid Red 52 0.08 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 18]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 2 parts

0.5 part of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.1 parts of the copolymer solution obtained in Synthesis Example 18

(A) Colorant: C.I. Acid Red 52 0.1 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

About each colored curable resin composition obtained in Examples 15-18, the film thickness measurement, chromaticity evaluation, and heat resistance evaluation were performed similarly to Examples 1-6 and Comparative Examples 1-2. A result is shown in Table 7. The larger the value of Y, the higher the brightness, and the smaller ΔEab*, the smaller the color change before and after heating, and the better the heat resistance.

[Example 19]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 31, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 20]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 32, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 21]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 33, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 22]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 34, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 23]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 35, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 24]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 36, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 25]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except for using the copolymer dispersion liquid obtained by the synthesis example 37, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 26]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except for using the copolymer dispersion liquid obtained by the synthesis example 38, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 27]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1 except for using the copolymer dispersion obtained in Synthesis Example 39 instead of the xanthene dye 1.

[Example 28]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 40, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 29]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 41, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 30]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 42, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 31]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the compound represented by Formula (aa11) obtained by Synthesis Example 43, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 32]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the compound represented by Formula (aa12) obtained by Synthesis Example 44, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 33]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the compound represented by Formula (aa13) obtained by Synthesis Example 45, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 34]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 0.8 parts

0.2 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 46

(A) Colorant: C.I. Acid Red 52 0.03 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 35]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 0.8 parts

0.2 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.0 parts of the copolymer solution obtained in Synthesis Example 47

(A) Colorant: C.I. Acid Red 52 0.04 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 36]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 0.8 parts

0.2 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 2.9 parts of the copolymer solution obtained in Synthesis Example 48

(A) Colorant: C.I. Acid Red 52 0.04 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

[Example 37]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 0.8 parts

0.2 parts of acrylic pigment dispersant

Propylene glycol monomethyl ether acetate 30 parts

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant (A3): 3.1 parts of the copolymer solution obtained in Synthesis Example 49

(A) Colorant: C.I. Acid Red 52 0.05 parts

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (IRgacure (registered trademark) OXEO1; manufactured by BASF)

(F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

About each colored curable resin composition obtained in Examples 34-37, the film thickness measurement, chromaticity evaluation, and heat resistance evaluation were performed similarly to Examples 1-6 and Comparative Examples 1-2. A result is shown in Table 8. The larger the value of Y, the higher the brightness, and the smaller ΔEab*, the smaller the color change before and after heating, and the better the heat resistance.

[Example 38]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 50, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 39]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 51, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 40]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except using the copolymer dispersion liquid obtained by the synthesis example 52, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 41]

(Preparation of colored curable resin composition)

Instead of the xanthene dye 1, except for using the copolymer dispersion liquid obtained by the synthesis example 53, it carried out similarly to Example 1, and obtained colored curable resin composition.

[Example 42]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1 except that Solvent Blue 38 (Orient Corp., Valifast blue 1605) was used instead of the xanthene dye 1.

[Example 43]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1 except that Solvent Blue 129 (Orient Corp., Valifast blue 100) was used instead of the xanthene dye 1.

[Example 44]

(Preparation of colored curable resin composition)

Using the compound represented by the formula (4-9) instead of the xanthene dye 1, also C.I. Except containing the pigment violet 23, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Example 45]

(Preparation of colored curable resin composition)

Using the compound represented by the formula (1-44) instead of the xanthene dye 1, also C.I. Except containing the pigment violet 23, it carries out similarly to Example 1, and obtains colored curable resin composition.

[Examples 46-50 and Comparative Examples 3-4]

(Preparation of colored curable resin composition)

(A) Colorant (A1): C.I. Pigment Blue 15:6 (pigment) 20 parts

3.9 parts of acrylic pigment dispersant

130 parts of propylene glycol monomethyl ether acetate

to sufficiently disperse the pigment using a bead mill, and

(A) Colorant: C.I. Acid Red 52 Amount shown in Table 9

(B) Resin: 50 parts of Resin B1 (in terms of solid content)

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayarad (registered trademark) DPHA; manufactured by Nippon Explosives Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzoyloxy-1-(4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1; manufactured by BASF) 10 parts

(F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) solvent: 556 parts of ethyl lactate

(E) solvent: 8 parts of propylene glycol monomethyl ether acetate

was mixed to obtain a colored curable resin composition.

About each colored curable resin composition obtained in Examples 46-50 and Comparative Examples 3-4, the film thickness measurement, chromaticity evaluation, and heat resistance evaluation were performed similarly to Examples 1-6 and Comparative Examples 1-2. A result is shown in Table 9. The larger the value of Y, the higher the brightness, and the smaller ΔEab*, the smaller the color change before and after heating, and the better the heat resistance.

The colored coating film and colored pattern formed from the colored curable resin composition of this invention have favorable heat resistance and favorable brightness. It turns out that the color filter formed from the colored curable resin composition of this invention is useful, and the liquid crystal display device containing the said color filter is excellent in a display characteristic.

Claims (9)

delete delete delete Triarylmethane dyes, blue pigments (A1) and C.I. A colorant comprising Acid Red 52, wherein the triarylmethane dye is a polymer, and the C.I. The coloring agent whose content of acid red 52 is 0.1-10 mass parts with respect to 100 mass parts of blue pigments (A1). 5. The method of claim 4,
The colorant in which a blue pigment (A1) contains CI pigment blue 15:6. 5. The method of claim 4,
The colorant in which a blue pigment (A1) consists only of CI pigment blue 15:6. The colored curable resin composition containing the coloring agent of Claim 4, resin (B), a polymeric compound (C), and a polymerization initiator (D). The color filter formed of the colored curable resin composition of Claim 7. A display device comprising the color filter according to claim 8 .