KR20160014542A - Colored curable resin composition - Google Patents

Abstract

Provided is a tinted curable resin composition, which forms a color filter having favorable thermal resistance and brightness, and which comprises a coloring agent (A), a resin (B), a polymeric compound (C), and a polymerization initiator (D). The coloring agent (A) includes a blue pigment (A1) and C.I. acid red 52. More particularly, the tinted curable resin composition comprises 0.1 to 10 parts by weight of C.I. acid red 52 based on 100 parts by weight of the blue pigment (A1). Desirably, the coloring agent (A) additionally comprises a blue or a purple pigment (A2).

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

The color filter formed from the colored curable resin composition is used in a display device such as a liquid crystal display panel, an electroluminescence panel, and a plasma display panel, and a color filter having good brightness, good contrast, and good resolution has been demanded. 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 coloring agent has been studied. However, it has been a problem that heat resistance, chemical resistance, and the like are lowered by containing a dye.

Patent Document 1 discloses that 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: When the content of the acid red 52 is higher than that of C.I. Pigment Blue 15: 6, based on 100 parts by mass of the colorant-curable resin composition.

Japanese Patent Application Laid-Open No. 2013-144724

The color filter formed from the above-mentioned colored curable resin composition can not always sufficiently satisfy both the heat resistance and the 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). Acid Red 52, and C.I. Wherein the content of the acid red 52 is 0.1 to 10 parts by mass relative to 100 parts by mass of the blue pigment (A1).

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

[3] The dye according to any one of [1] to [3], wherein the content of the blue or violet dye (A2) Is 80 to 10000 parts by mass relative to 100 parts by mass of Acid Red 52. The colored curable resin composition according to [2]

[4] A dye according to any one of [1] to [4], wherein the content of the blue or violet dye (A2) , And 80 to 1000 parts by mass with respect to 100 parts by mass of Acid Red 52. The colored curable resin composition according to [3]

[5] The process according to [1], wherein the blue pigment (A1) is C.I. [1] to [4], wherein the coloring curable resin composition comprises Pigment Blue 15: 6.

[6] The process according to [1], wherein the blue pigment (A1) The pigmented curable resin composition according to any one of [1] to [4], wherein the pigment is selected from the group consisting 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] A process for producing a colorant, wherein the blue pigment (A1) Pigment Blue 15: 6.

[9] The process according to [1], wherein the blue pigment (A1) is C.I. Pigment Blue 15: 6 ".

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

[11] A dye represented by the formula (A7) or a polymer comprising a constituent unit derived from the dye represented by the formula (A7), a blue pigment (A1) Colorant containing Acid Red 52.

[In the formula (A7)

g represents an arbitrary natural number.

And G ^{g -} represents anion of g.

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

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

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

[12] The process according to [12], wherein the blue pigment (A1) Pigment Blue 15: 6.

[13] A process for producing a colorant, wherein the blue pigment (A1) The colorant according to [11], which is composed of Pigment Blue 15: 6 alone.

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

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

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

According to the colored curable resin composition of the present invention, a color filter having good heat resistance and good brightness can be produced.

The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

The colored curable resin composition of the present invention preferably contains at least one selected from a solvent (E) and a leveling agent (F).

The colored curable resin composition of the present invention may contain a polymerization initiator (D1).

≪ Colorant (A) >

The colorant (A) contains the blue pigment (A1) and the C.I. Includes Acid Red 52.

C.I. The content of the acid red 52 is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and further preferably 1 to 8 parts by mass with respect to 100 parts by mass of the blue pigment (A1).

The colorant (A) may contain a blue or violet dye A2 (hereinafter also referred to as " dye A2 "). The colorant (A) may be a pigment different from the blue pigment (A1) (hereinafter also referred to as "pigment (Ad)"), a dye (Ac) different from the blue or purple dye (A2) Dye (Ac) ").

Further, in the present application, "C.I." means a color index (C.I.).

≪ Blue pigment (A1) >

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

Two or more kinds of blue pigments (A1) may be contained.

The blue pigment (A1) is a mixture of C.I. Pigment Blue 15: 6, and C.I. Pigment Blue 15: 6 is more preferable.

≪ Dye (A2) >

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

The blue or violet dye A2 is a dyestuff represented by the formula (A3), the triarylmethane dye (A4), the tetraazaporphyrin dye (A5), the anthraquinone dye (A6) (A7)), and it is preferably at least one selected from the group consisting of

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

More preferably at least one selected from the group consisting of a triarylmethane dye (A4) and a dye (A7).

Two or more of the dyes (A2) may be contained.

The xanthene dye (A3) is a dye containing a compound having a xanthene skeleton in its molecule.

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

Examples of the xanthene dye (A3) include commercially available xanthene dyes (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Juagai Kasei Co., Ltd., "Rhodamin 6G" manufactured by Daoka Chemical Industry Co., ). Further, commercially available xanthene dyes can also be synthesized as starting materials by referring to Japanese Patent Application Laid-Open No. 2010-32999.

The triarylmethane dye (A4) is a dye containing a compound having a triarylmethane skeleton in its molecule. As the triarylmethane dye (A4), for example,

C.I. Acid violet (hereinafter, abbreviated as C.I. Acid Violet) is used as a reference only.) 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, 93, 93, 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. Modern 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.

Examples of the triarylmethane dye (A4) include the compounds described below.

The tetraazaporphyrin dye (A5) is a dye containing a compound having a tetraazaporphyrin skeleton in its molecule. When the tetraazaporphyrin dye is an acidic dye or a basic dye, it may form a salt with any cation or anion.

The tetraazaporphyrin dyes include the compounds described below.

The anthraquinone dye (A6) is a dye containing a compound having an anthraquinone skeleton in a molecule.

As the 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, 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 the compounds described below.

Examples of the dye (A7) include a compound represented by the formula (A7) and tautomers thereof.

[In the formula (A7)

g represents an arbitrary natural number.

And G ^{g -} represents anion of g.

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

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

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

^Examples of the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include methyl group, ethyl group, n-propyl group, isopropyl group, A cyclopropyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, Cyclohexyl group, cyclohexyl 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, a norbornyl group, a methylnorbornyl group and an isobornyl group. Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

-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-.

Specific examples of the 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 are substituted with -O- The same can be said. Preferably, -CH ₂ - contained in an alkyl group having 1 to 10 carbon atoms is substituted with -O-, and more preferably -CH ₂ - included in an alkyl group having 1 to 6 carbon atoms is -O- Lt; / RTI >

^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, Atom or a 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, and further a hydrogen atom or a methyl group; More preferably 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 .

Examples of the aryl group which may have a substituent include an aryl group having 6 to 14 carbon atoms such as a phenyl group, a naphthyl group and an anthracenyl group, and examples of the substituent which the aryl group may have include a halogen atom and an alkyl group having 1 to 8 carbon atoms Alkyl group.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, A cyclohexyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, (Adamantanyl-1-yl) alkane-1-yl group, a cyclohexyl group, a cyclohexyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, An alkyl group having 1 to 20 carbon atoms such as a boronyl group, a methylnorbornyl group and an isobornyl group. -CH ₂ other than the - - -CH ₂ adjacent to the nitrogen atom contained in these alkyl groups, it is optionally substituted by a -O-, substituent which may have an alkyl group the art, an amino group, substituted amino group, a halogen atom and a silicon atom And the like.

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 those having 1 to 8 carbon atoms such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, sec-butylamino, tert- 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 methacryloyl group as a structural unit of a group.

The number of carbon atoms of the group containing an acryloyl group or a methacryloyl group is usually 3 to 30, preferably 3 to 20.

The group containing an acryloyl group or a methacryloyl group is preferably a group containing an acryloyloxy group or a methacryloyloxy group.

The group containing an acryloyl group or a methacryloyl group is preferably a group represented by the formula (A7-1).

[In the formula (A7-1), ^R15A 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-. * Represents the bonding bond with the nitrogen atom.

Examples of the alkanediyl group having 1 to 8 carbon atoms represented by R ^14A include methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl, pentane- A 1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, an ethane-1,1-diyl group, Diethyl group, pentane-2,4-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane- Methylenebutane-1,4-diyl group, preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, more preferably a methylene group .

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

^Examples of the optionally substituted amino group represented by R ^21A and R ^22A include a methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, tert- An amino group, an amino group, a hexylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, a diisopropylamino group, an ethylmethylamino group, an ethylisopropylamino group, an ethylpropylamino group, an isopropylmethylamino group, an isopropylpropylamino group, , Naphthylamino group, 2-methylphenylamino group, 4-methylphenylamino group, 3-methylphenylamino group, 3,5-dimethylphenylamino group, 4-ethylphenylamino group, N- N- (acryloyloxymethyl) -N-methylamino group, N- (acryloyloxyethyl) -N-ethylamino (Methacryloyloxyethyl) -N-ethylamino group, N- (acryloyloxyethyl) -N-phenylamino group, N- (acryloyloxyethyl) -N- (Methoxymethyl) amino group, N- (acryloyloxyethyloxymethyl) -N-ethylamino group and N- (methacryloyloxyethyloxymethyl) -N-ethylamino group.

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, a benzoisothiazolyl group , A thienyl group, and a benzothienyl group, and a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms containing at least one nitrogen atom or sulfur atom as a constituent of the ring is preferable.

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

The optionally substituted amino group may be the same as the optionally substituted amino group represented by R ^21A and R ^22A .

Examples of the alkyl group having 1 to 20 carbon atoms 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 .

Examples of the aryl group which may have a substituent include a phenyl group, a naphthyl group and an anthracenyl group, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; And an alkyl group having 1 to 20 carbon atoms.

The heteroaromatic hydrocarbon group represented by D is preferably a group represented by the formula (III).

[In the 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.

* Represents the bonding 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 have.

The aryl group which may have a substituent represented by R ⁵⁵ includes a phenyl group.

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

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

R ⁵⁶ is preferably an amino group which may be substituted.

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

g is an arbitrary natural number, preferably a natural number of 1 to 2, more preferably 1.

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

G ^{g -} is preferably a monovalent anion, and examples thereof include halide ions such as a fluoride ion, a chloride ion, a bromide ion and an iodide ion, an anion represented by the formula (y1) Anion represented by formula (y3) and 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), and R ^B2 and R ^B3 are, independently of each other, represent a halogen atom or a halogenated hydrocarbon group, or R ^B2 and R ^B3 are bonded to each other -SO ₂ -N ^- containing - -SO ₂ To form a ring.

In 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, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, , An octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

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

Examples of the halogenated alkyl group having 1 to 8 carbon atoms include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) - A 1,2,2,2-tetrafluoroethyl group, a perfluoropropyl group, a 1,1,2,2-tetrafluorobutyl group, a 1,1,2,2,3,3-hexafluorobutyl group , A 1,1,2,2,3,3,4,4-octafluorobutyl group, a perfluorobutyl group, a dibromomethyl group, and a tribromomethyl group, preferably having 1 to 8 carbon atoms Lt; / RTI >

Examples of the aromatic hydrocarbon group having a halogen atom of 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.

R ^B1 is preferably a halogenated alkyl group having 1 to 8 carbon atoms, more preferably a fluorinated alkyl group having 1 to 8 carbon atoms.

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, 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 and having a halogen atom.

Examples of the halogenated alkyl group having 1 to 8 carbon atoms include a difluoromethyl group, a trifluoromethyl group, a 1,1-difluoroethyl group, a 2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, Tetrafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl) - A 1,2,2,2-tetrafluoroethyl group, a perfluoropropyl group, a 1,1,2,2-tetrafluorobutyl group, a 1,1,2,2,3,3-hexafluorobutyl group , A 1,1,2,2,3,3,4,4-octafluorobutyl group, a perfluorobutyl group, a dibromomethyl group, and a tribromomethyl group, preferably having 1 to 8 carbon atoms Lt; / RTI >

Examples of the aromatic hydrocarbon group having a halogen atom of 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.

R ^B2 and R ^B3 are preferably the same groups.

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

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

R ^B4 and R ^B5 are preferably the same group.

Examples of anions represented by the formula (y1) include anions such as methanesulfonate anion, toluenesulfonate anion, dodecylbenzenesulfonate anion, trifluoromethanesulfonate anion, perfluorobutanesulfonate anion, phenylsulfonate anion, fluoro And phenylsulfonic acid anion.

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

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

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

The dye (A7) can be produced, for example, by the method described in Korean Patent Publication No. 2014-0026284.

The blue or violet dye may be a monomer or a polymer. The polymer which is a blue or purple dye is a polymer containing structural units derived from a blue or purple dye and may be a polymer consisting of only structural units derived from blue or purple dyes and may be a polymer composed of structural units derived from blue or purple dyes, (Hereinafter also referred to as copolymer (a) in some cases). The structural unit derived from the blue or purple dye may be a divalent or higher group formed by polymerization of a polymerizable blue or purple dye or may be a monovalent or higher group formed by removing one or more hydrogen atoms from a blue or purple dye. Examples of the copolymer (a) include, in addition to the structural unit derived from the blue or purple dye, a structural unit derived from a monomer having an ethylenically unsaturated bond and a structural unit represented by the following formulas (1) to (3) , And a copolymer containing at least one selected from the above.

The copolymer (a) may be a copolymer comprising a structural unit derived from a monomer which will induce the resin (B) described below and a structural unit derived from a blue or purple dye.

[In the formula (1), R ⁹ and R ¹⁰ each independently represent 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, Lt; / RTI > group or a combination thereof.

m 'represents an integer of 0 to 5.]

[In the formula (2), R ¹¹ represents 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, an alkylaryl group which may have a substituent, Combination.

R ¹² represents 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, -CO-R ¹⁷ -COOH, or a combination thereof.

R ¹⁷ represents an alkylene group having 1 to 30 carbon atoms which may have a substituent or an alkoxylene group having 1 to 30 carbon atoms which may have a substituent.

[In the formula (3), R ¹³ and R ¹⁴ each independently represent 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, Lt; / RTI > group or a combination thereof.

R ¹⁵ represents -COOH or -CONHR ¹⁸ .

R ¹⁸ represents an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 6 to 30 carbon atoms which may have a substituent.

R ¹⁶ represents -COOH, and R ¹⁵ and R ¹⁶ combine with 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 (based on the total weight of the monomers forming the copolymer (a) To 30% by weight.

Further, it may contain a structural unit derived from a monomer copolymerizable with a structural unit derived from a monomer having an ethylenic unsaturated bond. Specifically,

Alkenyl aromatic monomers such as styrene,? -Methylstyrene, vinyltoluene, and vinylbenzyl methyl ether;

Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Unsaturated carboxylic acid ester compounds such as 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;

Carboxylic acid vinyl 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 combinations thereof.

The structural unit derived from the blue or violet 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 the formula (A7) Is preferable.

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

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

The content of the dye (A2) is preferably in the range of C.I. Is generally 80 to 10000 parts by mass, preferably 80 to 7500 parts by mass, more preferably 80 to 1000 parts by mass, and still more preferably 80 to 600 parts by mass based on 100 parts by mass of the acid red 52. [

≪ Dye (Ac) and Pigment (Ad) >

The dye (Ac) is not particularly limited, and known dyes can be used.

The pigment (Ad) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the color index (The Society of Dyers and Colourists) are cited.

As the pigment, C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38, and the like.

The colorant (A) is preferably a colorant comprising the combination described below.

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

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

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the total amount of solid matter. When the content of the colorant (A) is within the above range, the color density when the color filter is formed is sufficient and the resin (B) and the polymerizable compound (C) can be contained in a required amount in the composition. Can be formed. Here, the "total amount of solid content" in the present specification means the amount excluding the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid content and the content of each component can be measured by a known analytical means such as liquid chromatography or gas chromatography.

≪ Resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

(A) (hereinafter sometimes referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4, A copolymer of a monomer (b) having an unsaturated bond (hereinafter sometimes referred to as " (b) ");

(Hereinafter sometimes referred to as "(c)") which is copolymerizable with the resin (K2) (a), (b) and (a) Copolymer;

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin (b) is reacted with the copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with the copolymer of (b) and (c);

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

Resin reacted with water.

(a) include, for example, 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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [2.2.1] hept-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 dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

(Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [(meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

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

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(b) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring) and an ethylenically unsaturated bond ≪ / RTI > (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(b1) 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.

(b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-1)"), alicyclic unsaturated And a monomer (b1-2) having a structure in which a hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Sucroide 2000; Daicel), 3,4-epoxycyclohexylmethyl Acrylate (for example, Cyclomer M100, manufactured by Daicel Co.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, I) and compounds represented by the formula (II).

[In the 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 hydroxy 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.

* Represents the hand of joining with O.]

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

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

As R ^a and R ^b , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are preferable, and a hydrogen atom and a methyl group are more preferable.

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, , 6-diyl group, and the like.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * - CH ₂ CH ₂ -O- (wherein * represents a bond with O).

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). (I-1), (I-3), (I-5), ). ≪ / RTI > More preferably, the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) can be mentioned.

Examples of the compound represented by formula (II) include compounds represented by formula (II-1) to formula (II-15). (II-1), II-3, II-5, II-7, II-9 or II- ). ≪ / RTI > More preferably, the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) can be mentioned.

The compound represented by the formula (1) and the compound represented by the formula (II) may be used alone. In addition, they can be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, more preferably from 20:90 to 90:10, in terms of the molar ratio, preferably in the formula (I) : 80 to 80:20.

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyloxetane, 3-methyl- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that the reliability of the obtained color filter can be further enhanced, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable because of excellent storage stability of the colored curable resin composition.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as "dicyclopentanyl (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Commonly referred to as " dicyclopentenyl (meth) acrylate " as the common name) (Meth) acrylate, propyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (Meth) acrylates such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cicarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2- ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance Do.

In the resin [K1], the ratio of the structural units derived from each other is preferably such that, among the total structural units constituting the resin [K1]

(a); 2 to 60 mol%

(b); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(b); 50 to 90 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the resulting color filter are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) It can be produced with reference to the cited documents.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are put into a reaction vessel and oxygen is replaced by, for example, nitrogen, thereby forming a deoxidized atmosphere. While stirring, . The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides such as benzoyl peroxide The solvent may be any one that dissolves the respective monomers, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later and the like.

As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition 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 other is preferably from 1 to 100,

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c); 1 to 65 mol%

, ≪ / RTI >

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c); 5 to 60 mol%

Is more preferable.

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 in forming the colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent There is a tendency.

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

In the resin [K3], the ratio of the respective structural units derived from the respective resins is, among the total structural units constituting the resin [K3]

(a); 2 to 60 mol%

(c); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(c); 50 to 90 mol%

Is more preferable.

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 obtained by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and / or carboxylic anhydride of (a) can do.

First, the copolymer of (a) and (c) is prepared in the same manner as the method described as the method for producing the resin [K1]. In this case, the proportion of the structural units derived from each of them is preferably the same as that in the examples of the resin [K3].

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

Subsequently to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced by air from nitrogen, and (b) a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (e.g., hydroquinone) are placed in a flask and reacted at 60 to 130 캜 for 1 to 10 hours, for example, to prepare resin [K4] .

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting the content within this range, there is a tendency that the balance between the storage stability of the colored curable resin composition, the developability in forming the pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern tends to be good. (B1) is more preferable, and (b1-1) is more preferable for the resin (K4) because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the introduction method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. Further, in the same manner as the polymerization conditions, the introduction method and the reaction temperature can be appropriately adjusted in consideration of the production facility and the amount of heat generated by polymerization.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production of resin [K1]. In the same manner as described above, the solution obtained after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) obtained by re-precipitation or the like may be used.

the proportion of the structural units derived from the structural units (b) and (c)

(b); 5 to 95 mol%

(c); 5 to 95 mol%

, ≪ / RTI >

(b); 10 to 90 mol%

(c); 10 to 90 mol%

Is more preferable.

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

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is more preferable, and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether is high and unreacted (b)

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxy group generated by the reaction of a cyclic ether and a carboxylic acid or a carboxylic acid anhydride.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / A resin [K1] such as an acrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin such as a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride in addition to the resin [K6] have.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution of the coloring pattern tends to be improved.

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

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, still more preferably 70 to 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of the solid components.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, Is a (meth) acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) (Meth) acrylate, tetrapentaerythritol hexa (meth) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta Ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, Acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate Caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

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

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and further preferably from 17 to 55% by mass, based on the total solid content. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be improved.

≪ Polymerization initiator (D) >

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

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

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- - ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1 -imine, N- acetoxy- 1- [ -9-ethyl-6- (2-methylbenzoyl) -9H-carbazole < / RTI > -3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure OXEO1, OXEO2 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. O-acyloxime compound is preferably selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable. If these O-acyloxime compounds are used, a color filter with a high lightness tends to be obtained.

The alkylphenone compound may be at least one selected from the group consisting of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one,?,? - diethoxyacetophenone and benzyldimethyl ketal. Irgacure 369, 907 and 379 (manufactured by BASF) can be used.

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

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra -Chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204 ), Imidazole compounds in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A 7-10913).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, 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-ethyl anthraquinone, camphorquinone, etc .; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator D1 (particularly amines) described below.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Onium salts such as phenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates and benzoin tosylates.

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

≪ Polymerization initiator (D1) >

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

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- -Bis (ethylmethylamino) benzophenone, and among these, 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Oxanone, and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When the polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Mass part. When the amount of the polymerization initiator (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and solvents commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide 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, Butyl propionate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and? -Butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene 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, And the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether Teracetate and diethylene glycol monobutyl ether acetate, and the like.

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

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 these solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solids of the color-curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristics are not insufficient when the color filter is formed, so that the display characteristics tend to be good.

≪ Leveling agent (F) >

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

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, TORAY Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, 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 Co., Ltd.) .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is possible to use a flour (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, (Manufactured by Mitsubishi Materials Corporation), RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, EF303, EF351 and EF352 ) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

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

The content of the leveling agent (F) is preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.01 mass% or less, relative to the total amount of the colored curable resin composition. Or more and 0.05 mass% or less. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be improved.

≪ Other components >

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

≪ Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be obtained by using, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) F), a polymerization initiator (D1), and other components.

The dye (A2) and, if necessary, the dye (Ac) to be used may be dissolved in a part or all of the solvent (E) beforehand to prepare a solution. It is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 mu m.

The blue pigment (A1) is preferably mixed with a part or all of the solvent (E) and dispersed by using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or the whole of the pigment dispersant and the resin (B) may be blended. The desired colored curable resin composition can be prepared by mixing the remaining components in the thus obtained pigment dispersion to a predetermined concentration.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 mu m.

According to the colored curable resin composition of the present invention, a color filter having excellent heat resistance can be produced. Such a color filter is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

[Example]

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by examples. In the examples, "% " and " part " are by mass% and part by mass unless otherwise specified.

In the following Synthesis Examples, the compounds were identified by mass analysis (LC: Agilent 1200 type, MASS: Agilent LC / MSD type) or elemental analysis (VARIO-EL;

[Synthesis Example 1]

20 parts of the compound represented by the 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 obtained 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 the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected as a residue of suction filtration and 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 the compound represented by the formula (1-24);

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

                        Exact Mass: 602.2

[Synthesis Example 2]

15 parts of a mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name: Chugai Aminol Fast Pink R) (manufactured by Sekisui Chemical Co., Ltd.) was added to a flask equipped with a stirrer, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature below 20 占 폚 with stirring. After completion of the dropwise addition, the temperature was raised to 50 占 폚, maintained at the same temperature for 5 hours for reaction, and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while maintaining the temperature at 20 캜 or lower with stirring. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was subjected to solvent distillation with a rotary evaporator, followed by addition of a small amount of methanol, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain the compound represented by the formula (Aa-1-1) to (Aa-1-8) Mixture).

[Synthesis Example 3]

The following reaction was carried out in a nitrogen atmosphere. 36.3 parts of potassium thiocyanate and 160.0 parts of acetone were put into a flask equipped with a condenser and a stirrer, followed by stirring at room temperature for 30 minutes. Subsequently, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, the reaction mixture was ice-cooled, and 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, the reaction mixture was ice-cooled, and 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 35.3 parts of chloroacetic acid at room temperature was added dropwise. After completion of dropwise addition, the mixture was stirred for 7 hours under reflux. Subsequently, the reaction mixture was allowed to cool to room temperature, and then the reaction solution was taken up in 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Thereafter, stirring was stopped, and the mixture was allowed to stand for 30 minutes, but the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by separating 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 saline. An appropriate amount of sodium sulfate 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 subjected to solvent evaporation using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 캜 under reduced pressure to obtain 52.0 parts of a compound represented by the formula (B-I-1). Yield 50%

The following reaction was carried out in a nitrogen atmosphere. 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 were added to a flask equipped with a stirrer, Followed by the addition of 14.8 parts of phosphorus oxychloride, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Stirring was continued, and the mixture was allowed to stand for 30 minutes, and then the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of gum was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation with an equalizer to obtain a bluish green solid. Further, the violet solid was dried under reduced pressure at 60 占 폚 to obtain 19.8 parts of a compound represented by the formula (A-I-a1). Yield 100%

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

(Mass analysis) Ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺

                        Exact Mass: 636.3

The following reaction was carried out in a nitrogen atmosphere. 10.0 parts of a compound represented by the formula (AI-a1), 4.5 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) N-dimethylformamide (100.0 parts) were added, and the mixture was stirred at 50 to 60 ° C for 3 hours. Subsequently, the reaction mixture was cooled to room temperature, and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to obtain a bluish green solid. Further, the cyan-green solid was dried under reduced pressure at 60 占 폚 to obtain 11.3 parts of a compound represented by the formula (A-I-a9). Yield 82%

[Synthesis Example 4]

Nitrogen was flowed at 0.02 L / min in a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 46 parts by mass of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) 50: 50) were dissolved in 185 parts by mass of ethyl lactate to prepare a solution, and the resulting solution was added dropwise to a flask maintained at 70 DEG C over 4 hours using a dropping funnel.

On the other hand, a solution obtained by dissolving 30 parts by mass of 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, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature. The weight average molecular weight Mw was 9.1 x 10 ³ , the molecular weight distribution was 2.1, the solid content was 26% 120 mg-KOH / g of resin B1 solution was obtained. Resin B1 has the following structural unit.

[Synthesis Example 5]

182 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to nitrogen. After raising the temperature to 100 DEG C, 22.0 parts of mono-methacrylate of tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) and 136 parts of propylene glycol monomethyl ether acetate was added to a mixture of 70.5 parts of acrylate, 43.0 parts of methacrylic acid, And 3.6 parts of azobisisobutyronitrile was added dropwise, and further stirring was continued at 100 占 폚.

Next, 35.5 parts of glycidyl methacrylate (0.25 mol, (50 mol% based on the carboxyl group of the methacrylic acid used in the present reaction)) and 0.9 part of trisdimethylaminomethylphenol And 0.145 parts of hydroquinone were charged into a flask, and the reaction was continued at 110 캜 to obtain a resin B2 solution having a solid content of 29% and an acid value of solid content of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in Synthesis Example were measured by the GPC method under the following conditions.

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 Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained as described above was defined as a molecular weight distribution.

[Synthesis Example 6]

To 28.52 parts of bis-N-ethyl-N-hydroxyethylaminobenzophenone and 17.80 parts of triethylamine, 50 mL of dichloromethane was added and dissolved by stirring. Thereafter, 13.56 parts of methacrylic anhydride was added, and the temperature was raised to 40 占 폚 and held. After the completion of the reaction, the reaction mixture was cooled to room temperature, water was added thereto, the layers were separated, 20 mL of a saturated sodium chloride solution was added, and the mixture was stirred for 30 minutes. After layer separation, the organic layer was distilled off, and the remaining solid was dried under reduced pressure to obtain 21.4 parts of a compound represented by the formula (aa2).

21.4 parts of the compound represented by the formula (aa2) was added to 500 mL of chloroform and stirred. Then, 49.08 parts of phosphorus oxychloride was added and stirred for 15 minutes. 14.56 parts of N-phenyl-1-naphthylamine was added, and the mixture was refluxed. After completion of the reaction, the mixture was cooled to room temperature, water was added, and the mixture was stirred. After stirring, the mixture was allowed to stand to separate layers, and the organic layer was distilled off. The remaining solid was dried under reduced pressure and purified to obtain 20.3 parts of a 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 and dissolved, and then 2.50 parts of sodium trifluoromethanesulfonate was added to replace the salt. After filtration, the resulting compound was washed with water, and the remaining solid was dried under reduced pressure to obtain 5.5 parts of a compound represented by the formula (aa4).

[Synthesis Example 8]

10.00 parts of the compound represented by the formula (aa3) was added to 100 mL of methanol and dissolved, and 2.09 parts of lithium bistrifluoromethanesulfonimide was added to replace the salt. After filtration, the obtained compound was washed with water and dried under reduced pressure to obtain 7.5 parts of a compound represented by the formula (aa5).

[Synthesis Example 9]

30 parts of methyl ethyl ketone was added in a nitrogen atmosphere, and the temperature was raised to 70 占 폚. 2.54 parts of the compound represented by the formula (aa4), 0.16 part of 2,2'-azobisisobutyronitrile and 20 parts of methyl ethyl ketone, and the mixture was kept at 70 ° C for 3 hours. After completion of the addition, the mixture was maintained at 70 DEG C for 8 hours, and a part of methyl ethyl ketone was condensed. The reaction solution was then added to hexane, and the crystals were precipitated and filtered. The resulting solid was washed with hexane and dried under reduced pressure To obtain 1.80 parts of a polymer compound (aa4).

[Synthesis Example 10]

30 parts of methyl ethyl ketone was added in a nitrogen atmosphere, and the temperature was raised to 70 占 폚. 2.54 parts of the compound represented by the formula (aa4), 0.25 part of 2,2'-azobisisobutyronitrile, 0.51 part of benzyl methacrylate, 0.51 part of methacrylic acid and 0.42 part of N-phenylmaleimide were dissolved in 50 parts of methyl ethyl ketone And the mixture was kept at 70 DEG C for 3 hours. After completion of the addition, the mixture was maintained at 70 DEG C for 8 hours, and a part of methyl ethyl ketone was condensed. The reaction solution was then added to hexane, and the crystals were precipitated and filtered. The resulting solid was washed with hexane and dried under reduced pressure To obtain 2.35 parts of a polymer compound (aa4 ').

[Synthesis Example 11]

30 parts of methyl ethyl ketone was added in a nitrogen atmosphere, and the temperature was raised to 70 占 폚. 2.54 parts of the compound represented by the formula (aa5), 0.16 part of 2,2'-azobisisobutyronitrile and 20 parts of methyl ethyl ketone, and the mixture was charged into the reactor at 70 ° C. for 3 hours. After completion of the addition, the mixture was maintained at 70 DEG C for 8 hours, and a part of methyl ethyl ketone was condensed. The reaction solution was then added to hexane, and the crystals were precipitated and filtered. The resulting solid was washed with hexane and dried under reduced pressure To obtain 1.63 parts of a polymer compound (aa5).

[Synthesis Example 12]

In a nitrogen atmosphere, 30 parts of methyl ethyl ketone was added, and the temperature was raised to 70 占 폚. 2.54 parts of the compound represented by the formula (aa5), 0.25 part of 2,2'-azobisisobutyronitrile, 0.51 part of benzyl methacrylate, 0.51 part of methacrylic acid and 0.42 part of N-phenylmaleimide were dissolved in 50 parts of methyl ethyl ketone Dissolve in the reactor and keep it at 70 캜 for 3 hours. After completion of the addition, the mixture was maintained at 70 ° C for 15 hours, and methyl ethyl ketone was partially concentrated. The reaction solution was then added to hexane, and the crystals were precipitated and filtered. The resulting solid was dried under reduced pressure to obtain a polymer compound (aa5 ' ).

[Synthesis Example 13]

5.00 parts of the compound represented by the formula (aa3) was added to 50 mL of methanol and dissolved, and then 1.46 parts of sodium p-toluenesulfonate was added to replace the salt. After filtration, the obtained compound is washed with water and dried under reduced pressure to obtain 2.84 parts of a compound represented by the formula (aa6).

[Synthesis Example 14]

C.I. 5.00 parts of Basic Blue 26 was dissolved in 50 mL of methanol, and 2.10 parts of sodium p-toluenesulfonate was added to replace the salt. After filtration, the resulting compound is washed with water and dried under reduced pressure to obtain 2.71 parts of a 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 also referred to as a dye Dy), benzyl methacrylate, methacrylic acid, methyl methacrylate, and N-benzyl maleimide Was added in a weight ratio shown in Table 1, and 6 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) (initiator) was added to 100 parts by weight of the total amount of the monomers. Subsequently, 300 parts by weight of propylene glycol monomethyl ether acetate was added to 100 parts by weight of the total amount of the initiator and the monomer, followed by gradually stirring under a nitrogen atmosphere. The reaction solution was heated to 90 DEG C and stirred for 10 hours to obtain a copolymer.

[Synthesis Example 19-22]

Benzyl methacrylate, methacrylic acid, methyl methacrylate and N-benzyl maleimide represented by the formula (aa8) were put into a flask equipped with a cooling tube and a stirrer at the weights shown in Table 2, respectively, As the initiator, 2,2'-azobis (2,4-dimethylvaleronitrile) was added in an amount of 6 parts by weight based on 100 parts by weight of the total amount of the monomers. Subsequently, 100 parts by weight of the total amount of the initiator and the monomer was mixed with propylene glycol 300 parts by weight of monomethyl ether acetate (PGMEA) was added, and stirring was started slowly under a nitrogen atmosphere. The reaction solution was heated to 90 占 폚 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 Example 19-22 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, 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 wt% of each copolymer solution prepared in Synthesis Example 19-30, 12 wt% of blue pigment (BASF, B 15: 6), 6 wt% of dispersant (BYK, Diperbyk 6919) and 78.5 wt% of propylene glycol monomethyl ether acetate By weight, and dispersed using a paint shaker for 24 hours to prepare respective copolymer dispersions 1 to 12.

[Synthesis Example 43]

To the reactor were added 25 parts of pararosaniline hydrochloride and 500 parts of ethanol, and the mixture was stirred at 200 占 폚 for 8 hours. Then, the temperature of the solution was lowered to 25 ° C, and 174 parts of 2-methyl-2-propenoic-carboxyoxy ethyl ester was slowly added dropwise to the solution over 5 hours. Subsequently, the temperature of the solution was raised to 70 캜 and stirred for 24 hours. After the reaction was completed, the solution was slowly recrystallized with ethanol to obtain 54.5 parts of a compound represented by the formula (aa11).

[Synthesis Example 44]

To the reactor, 25 parts of para-rosaniline hydrochloride and 500 parts of ethanol were added, and the mixture was stirred at 200 占 폚 for 8 hours.

Subsequently, the temperature is lowered to 25 DEG C, and 209 parts of 2-methyl-2-propenoic-sulfamino ethyl ester is slowly added dropwise to the solution over 5 hours. Subsequently, the temperature of the solution was raised to 70 캜 and stirred for 24 hours.

After the reaction was completed, the solution was slowly recrystallized with ethanol to obtain 58.2 parts of a compound represented by the formula (aa12).

[Synthesis Example 45]

Synthesis was conducted in the same manner as in Synthesis Example 6 except that the compound represented by the formula (BI-1) was used instead of the N-phenyl-1-naphthylamine 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, except that the monomer represented by the formula (aa13) was used instead of the monomer represented by the formula (aa8).

[Synthesis Examples 50-53]

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

[Example 1]

(Preparation of colored curable resin composition)

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

Acrylic pigment dispersant   3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A5): A compound represented by the formula (2-29) 1.3 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate , And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A6): A compound represented by the formula (3-11) 1.3 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A7): A compound represented by the formula (A-I-a9) 1.8 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A3): xanthene dye 2 2.2 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 copies

Acrylic pigment dispersant 3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A3): xanthene dye 2 2.3 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were mixed to obtain a colored curable resin composition.

≪ Preparation of colored pattern >

The colored curable resin composition was coated on a glass substrate (Eagle 2000; Corning) having 5 cm corners by spin coating, and then pre-baked at 100 ° C for 3 minutes to obtain a colored layer. After cooling down, an exposure amount (based on 365 nm) of 150 mJ / cm 2 was measured in an atmospheric environment using an exposure apparatus (TME-150RSK; manufactured by Topcon Co., Ltd.) with a distance between the substrate on which the colored layer was formed and a quartz glass photomask, . As the photomask, a 100 μm line and space pattern was formed. The colored layer after light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 DEG C for 60 seconds, washed with water and then postbaked at 200 DEG C for 30 minutes in an oven To obtain a colored pattern.

≪ Measurement of film thickness &

With respect to the obtained coloring pattern, the film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.)).

≪ Evaluation of color &

Spectroscopy was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) in the XYZ color system of CIE were measured using the characteristic function of the C light source ) And three stimulus values Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 6.

[Heat resistance evaluation]

The coating film of the obtained colored curable resin composition was heated at 230 占 폚 for 20 minutes and the color difference? Eab * before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; OLYMPUS). As a result of evaluating the heat resistance of the obtained coating film, the color difference (Eab *) is shown in Table 6. [ The smaller the? Eab *, the smaller the color change before and after heating, and the better the heat resistance.

[Example 7]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1 except that the compound represented by the formula (aa4) obtained in the synthesis example 7 is used instead of the xanthene dye 1.

[Example 8]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the compound represented by formula (aa5) obtained in Synthesis Example 8 is used instead of the xanthene dye 1.

[Example 9]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1 except that the polymer compound (aa4) obtained in Synthesis Example 9 is used instead of the xanthene dye 1.

[Example 10]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the polymer compound (aa4 ') obtained in Synthesis Example 10 is used instead of the xanthene dye 1.

[Example 11]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the polymer compound (aa5) obtained in Synthesis Example 11 is used instead of the xanthene dye 1.

[Example 12]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1 except that the polymer compound (aa5 ') obtained in Synthesis Example 12 was used instead of the xanthene dye 1.

[Example 13]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1 except that the formula (aa6) obtained in Synthesis Example 13 is used instead of the xanthene dye 1.

[Example 14]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the polymer compound (aa7) obtained in Synthesis Example 14 is used instead of the xanthene dye 1.

[Example 15]

(Preparation of colored curable resin composition)

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

Acrylic pigment dispersant 0.5 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A3): The copolymer solution obtained in Synthesis Example 15 3.2

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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)   Part 2

Acrylic pigment dispersant 0.5 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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)   Part 2

Acrylic pigment dispersant 0.5 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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)   Part 2

Acrylic pigment dispersant 0.5 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A3): The copolymer solution obtained in Synthesis Example 18 3.1 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were mixed to obtain a colored curable resin composition.

Each of the colored curable resin compositions obtained in Examples 15 to 18 was subjected to film thickness measurement, chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2. The results are shown in Table 7. The larger the value of Y, the higher the brightness. 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)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 31 is used instead of the xanthene dye 1.

[Example 20]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 32 is used instead of the xanthene dye 1.

[Example 21]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 33 is used instead of the xanthene dye 1.

[Example 22]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 34 was used instead of the xanthene dye 1.

[Example 23]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 35 is used instead of the xanthene dye 1.

[Example 24]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 36 is used instead of the xanthene dye 1.

[Example 25]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 37 was used instead of the xanthene dye 1.

[Example 26]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 38 is used instead of the xanthene dye 1.

[Example 27]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 39 is used instead of the xanthene dye 1.

[Example 28]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 40 is used instead of the xanthene dye 1.

[Example 29]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1 except that the copolymer dispersion obtained in Synthesis Example 41 was used instead of the xanthene dye 1.

[Example 30]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 42 is used instead of the xanthene dye 1.

[Example 31]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the compound represented by the formula (aa11) obtained in Synthesis Example 43 is used instead of the xanthene dye 1.

[Example 32]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the compound represented by the formula (aa12) obtained in Synthesis Example 44 is used instead of the xanthene dye 1.

[Example 33]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1, except that the compound represented by the formula (aa13) obtained in Synthesis Example 45 was used instead of the xanthene dye 1.

[Example 34]

(Preparation of colored curable resin composition)

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

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 part

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 part

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A3): The copolymer solution obtained in Synthesis Example 48 2.9 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were 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 part

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

(A) Colorant (A3): The copolymer solution obtained in Synthesis Example 49 3.1 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXEO1 manufactured by BASF)  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were mixed to obtain a colored curable resin composition.

Each of the colored curable resin compositions obtained in Examples 34 to 37 was subjected to film thickness measurement, chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2. The results are shown in Table 8. The larger the value of Y, the higher the brightness. 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)

A colored curable resin composition is obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 50 is used instead of the xanthene dye 1.

[Example 39]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 51 was used instead of the xanthene dye 1.

[Example 40]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 52 was used instead of the xanthene dye 1.

[Example 41]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 1, except that the copolymer dispersion obtained in Synthesis Example 53 was used instead of the xanthene dye 1.

[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)

The use of the compound represented by the formula (4-9) instead of the xanthene dye 1, and the use of the compound represented by the formula C.I. A pigmented curable resin composition is obtained in the same manner as in Example 1, except that Pigment Violet 23 is contained.

[Example 45]

(Preparation of colored curable resin composition)

The use of a compound represented by the formula (1-44) instead of the xanthene dye 1, and the use of a compound represented by the formula C.I. A pigmented curable resin composition is obtained in the same manner as in Example 1, except that Pigment Violet 23 is contained.

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

(Preparation of colored curable resin composition)

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

Acrylic pigment dispersant   3.9 part

Propylene glycol monomethyl ether acetate 130 copies

And the pigment was thoroughly dispersed using a bead mill. Subsequently,

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

(Kayalad (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)  50 parts

(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE O1,  10 copies

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

(E) Solvent: Ethyl lactate 556 part

(E) Solvent: Propylene glycol monomethyl ether acetate   Part 8

Were mixed to obtain a colored curable resin composition.

Each of the colored curable resin compositions obtained in Examples 46 to 50 and Comparative Examples 3 to 4 was subjected to film thickness measurement, chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 6 and Comparative Examples 1 and 2. The results are shown in Table 9. The larger the value of Y, the higher the brightness. The smaller ΔEab *, the smaller the color change before and after heating, and the better the heat resistance.

The colored coating film or colored pattern formed from the colored curable resin composition of the present invention has good heat resistance and good brightness. A color filter formed of the colored curable resin composition of the present invention is useful, and a liquid crystal display device including the color filter is excellent in display characteristics.

Claims (9)

A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D). Acid Red 52, and C.I. Wherein the content of the acid red 52 is 0.1 to 10 parts by mass relative to 100 parts by mass of the blue pigment (A1). The method according to claim 1,
Wherein the blue pigment (A1) comprises CI Pigment Blue 15: 6. The method according to claim 1,
Wherein the blue pigment (A1) is composed only of CI Pigment Blue 15: 6. Triarylmethane dyes, blue pigments (A1) and C.I. A colorant comprising Acid Red 52, wherein the triarylmethane dye is a polymer, and C.I. Wherein a content of the acid red 52 is 0.1 to 10 parts by mass relative to 100 parts by mass of the blue pigment (A1). 5. The method of claim 4,
Wherein the blue pigment (A1) comprises CI Pigment Blue 15: 6. 5. The method of claim 4,
And the blue pigment (A1) is composed only of CI Pigment Blue 15: 6. A colored curable resin composition comprising a colorant according to any one of claims 4 to 6, a resin (B), a polymerizable compound (C) and a polymerization initiator (D). A color filter formed by the colored curable resin composition according to any one of claims 1 to 7. A display device comprising the color filter according to claim 8.