KR102003142B1 - Colored curable resin composition - Google Patents

Abstract

［식 중, ｋ１, ｋ２, ｋ３ 및 ｋ４는, 각각 독립하여, ０~４의 정수를 나타내고, １≤ｋ１＋ｋ２＋ｋ３＋ｋ４≤１６이다.
　Ｘ_ａ ^－, Ｘ_ｂ ^－, Ｘ_ｃ ^－ 및 Ｘ_ｄ ^－는, 각각 독립하여, －ＣＯ_３ ^－ 또는 －ＳＯ_３ ^－를 나타낸다.
　Ａ_ａ ^＋, Ａ_ｂ ^＋, Ａ_ｃ ^＋ 및 Ａ_ｄ ^＋는, 각각 독립하여, 나트륨 이온, 칼륨 이온 또는 식（ｂ）로 표시되는 카티온을 나타낸다.

식（ｂ）중, Ｒ^１００, Ｒ^１０１, Ｒ^１０２ 및 Ｒ^１０３는, 각각 독립하여, 수소 원자 또는 탄소수 １~３０의 탄화수소기를 나타낸다.］A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D)
Wherein the colorant (A) comprises a compound represented by the formula (a)
At least one selected from the group consisting of xanthene dyes and salts of xanthene dyes and cyanine dyes.

Wherein k1, k2, k3 and k4 independently represent an integer of 0 to 4, and 1? K1 + k2 + k3 + k4? 16.
X _a ^- , X _b ^- , X _c ^- and X _d ^- each independently represent -CO ₃ ^- or -SO ₃ ^- .
A _a ⁺ , A _b ⁺ , A _c ⁺ and A _d ⁺ each independently represent a sodium ion, a potassium ion or a cation represented by the formula (b).

In the formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² And R ¹⁰³ independently represent a hydrogen atom or a hydrocarbon group of 1 to 30 carbon atoms.

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

A color filter formed of a 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 is required.

In order to realize a color filter having good brightness, good contrast, and good resolution, a colored curable resin composition containing a dye as a colorant has been studied. However, it has been a problem that heat resistance and chemical resistance are lowered by containing a dye.

Patent Document 1 discloses a colored curable resin composition comprising C.I. Pigment Blue 15: 6, C.I. Acid Red 52 and a dye represented by the following formula as a colorant, wherein the content of C.I. Acid Red 52 , Which is 14.7 parts by mass based on 100 parts by mass of C. I. Pigment Blue 15: 6.

Japanese Patent Application Laid-Open No. 2013-144724

The color filter formed of the above-mentioned colored curable resin composition can not necessarily satisfy both heat resistance and lightness.

The present invention includes the following inventions.

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

Wherein the colorant (A) comprises a compound represented by the formula (a)

At least one selected from the group consisting of xanthene dyes and salts of xanthene dyes and cyanine dyes.

In the formula, k1, k2, k3 and k4 each independently represent an integer of 0 to 4, and 1k1 + k2 + k3 + k4? 16.

X _a ^- , X _b ^- , X _c ^- and X _d ^- each independently represent -CO ₃ ^- or -SO ₃ ^- .

A _a ⁺ , A _b ⁺ , A _c ⁺ and A _d ⁺ each independently represent a sodium ion, a potassium ion or a cation represented by the formula (b).

In the formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² And R ¹⁰³ independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

[2] The colored curable resin composition according to [1], wherein the xanthene dye is a C.I. acid 52 or a compound represented by the following formula (I).

[In the formula (I), R ¹ , R ² , R ³ And R ⁴ each independently represent a monovalent saturated hydrocarbon group having 2 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent.

R ⁵¹ , R ⁵² And R ⁵³ is independently a hydrogen atom, -SO _3, respectively ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.

X ⁺ and Z ⁺ each independently represent ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ , and R ¹³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ may be the same or different.

and a represents an integer of 1 to 4.]

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

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) may be a compound represented by the formula (a) (hereinafter sometimes referred to as a compound (a)),

Xanthene dyes, and salts of xanthene dyes and cyanine dyes.

The colorant (A) may also contain a blue or violet dye A2 (hereinafter sometimes referred to as " dye A2 "). The colorant (A) may also contain a dye (Ac) (hereinafter sometimes referred to as "dye (Ac)") different from the pigment (A1) and the blue or violet dye (A2).

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

≪ Compound (a) >

In the formula, k1, k2, k3 and k4 each independently represent an integer of 0 to 4, and 1k1 + k2 + k3 + k4? 16.

X _a ^- , X _b ^- , X _c ^- and X _d ^- each independently represent -CO ₃ ^- or -SO ₃ ^- .

A _a ⁺ , A _b ⁺ , A _c ⁺ and A _d ⁺ each independently represent a sodium ion, a potassium ion or a cation represented by the formula (b).

In the formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² And R ¹⁰³ independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 6 to 30 carbon atoms.

k1, k2, k3 and k4 independently represent an integer of 0 to 4; However, it is preferable that 1k1 + k2 + k3 + k4? 16 and 1? K1 + k2 + k3 + k4? 2.

R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² And R ¹⁰³ are preferably methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an iso-propyl group, a n-hexyl group, a n-hexyl group, (Branched?) Alkyl group having 3 to 30 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, And an alicyclic saturated hydrocarbon group having 3 to 30 carbon atoms such as decyl group. Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.

Specific examples of the compound (a) include those described below.

The content of the compound (a) is usually 0.1 to 99% by mass, preferably 0.1 to 20% by mass, and more preferably 0.1 to 10% by mass based on the total amount of the colorant (A) .

The compound (a) may contain two or more compounds.

<Xanthan Dye>

The xanthene dye means a dye comprising a compound having a xanthene skeleton. The xanthene dyes are preferably xanthene dyes having two -SO ₃ ^- groups as substituents, and C.I. acid red 52 and its exudate (s) are more preferable. The flexible body of C.I. Acid Red 52 means a compound represented by the formula (I) (hereinafter sometimes referred to as a compound (I)).

&Lt; Compound (I) &gt;

[In the formula (I), R ¹ , R ² , R ³ And R ⁴ each independently represent a monovalent saturated hydrocarbon group having 2 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent.

R ⁵¹ , R ⁵² And R ⁵³ is, independently, a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ .

X ⁺ and Z ⁺ each independently represent ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ , and R ¹³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ may be the same or different.

and a represents an integer of 1 to 4.]

R ¹ , R ² , R ³ And monovalent saturated hydrocarbon groups of 2 to 10 carbon atoms represented by R ⁴ include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert- n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, A straight chain or branched chain alkyl group having 3 to 10 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, a heptyl group, a 2-ethylhexyl group and a 1,1,5,5-tetramethylhexyl group; And a cycloalkyl group having 3 to 10 carbon atoms such as an adamantyl group, and an n-propyl group, an n-butyl group and a 2-ethylhexyl group are preferable.

R ¹ , R ² , R ³ And the hydrogen atom contained in the monovalent saturated hydrocarbon group of 2 to 10 carbon atoms represented by R &lt; ⁴ &gt; may be substituted with a hydroxy group, an alkoxy group or a halogen atom.

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

Examples of the alkoxy group include a carbon number such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2- An alkoxy group having 1 to 20 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom include a heptafluoropropyl group, a 1,1-difluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group , 2,2-difluorobutyl group, undecafluoropentyl group, 3- (trifluoromethyl) -3,4,4,4-pentafluorobutyl group, 6,6,6-trifluoro Hexyl group, heptachloropropyl group, heptabromopropyl group, 3,3,3-triiodopropyl group, 2,2-dichloro-3,3,3-trifluoropropyl group and the like, and preferably Is preferably a group represented by the following formula.

(* Indicates a combined hand.)

R ¹ , R ² , R ³ Examples of the aryl group represented by R &lt; ⁴ &gt; include an aromatic hydrocarbon group having 6 to 10 carbon atoms such as a phenyl group and a naphthalene group; and an aralkyl group having 6 to 10 carbon atoms such as a benzyl group and a phenethyl group.

R ¹ , R ² , R ³ And the aryl group represented by R &lt; ⁴ &gt; An alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group or an n-propyl group; an alkyl group having 1 to 20 carbon atoms such as a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, An alkoxy group having 1 to 20 carbon atoms such as a siloxane group and an icosyloxy group, or a hydroxy group.

R ¹ , R ² , R ³ And R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the monovalent saturated hydrocarbon group of 1 to 20 carbon atoms represented by R ¹³ include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- , a straight chain alkyl group having 1 to 20 carbon atoms such as an n-nonyl group, an n-decyl group, a n-dodecyl group, an n-hexadecyl group and an n-icosyl group, a branched chain alkyl group having 3 to 20 carbon atoms such as a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, And an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclodecyl group.

Z ⁺ represents a N ^{+ (R} _{13) 4,} Na ⁺ or K ^{+, R 13} can be the same or different.

-SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹³ ) ₄ .

R ¹ , R ² , R ³ And R ⁴ are each independently preferably an alkyl group having 3 to 10 carbon atoms or a phenyl group optionally having a substituent and more preferably a phenyl group optionally substituted with an alkyl group having 3 to 8 carbon atoms or an alkyl group having 1 to 10 carbon atoms .

R ¹ , R ² , R ³ And R ⁴ , R ¹ and R ³ are preferably the same groups, and it is preferable that R ² and R ⁴ are the same group.

a represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

R ⁵¹ , R ⁵² And R ⁵³ are preferably the same and more preferably all hydrogen atoms.

The compound (I) can be produced, for example, according to WO2013 / 050431.

Specific examples of the xanthene dyes include the following compounds in addition to C.I. Wherein R &lt; ²⁶ &gt; And R ⁴⁰ each independently 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 Chugai Chemical Industry Co., Ltd., "Rhodamin 6G" manufactured by Daoka Chemical Industry Co., ) And the compounds described below. Further, a commercially available xanthene dye can be used as a starting material and synthesized with reference to Japanese Patent Application Laid-Open No. 2010-32999.

The content of the xanthene dye is usually 0.1 to 30 parts by mass, preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass based on 100 parts by mass of the compound (a).

Two or more xanthene dyes may be included.

<Salts of xanthan dyes and cyanine dyes>

The salts of xanthine dyes and cyanine dyes are salts comprising anions derived from xanthene compounds and cations derived from cyanine compounds.

The cyanine compound refers to a compound having in its molecule a structure in which two heterocyclic rings are conjugated double bonds (conjugated double bonds) with an odd number of methine groups.

Examples of the anions derived from the xanthene compound include the anions derived from the above xanthene dyes.

As the cyanine compound, a compound represented by the formula (1b) or a compound represented by the formula (1c) is preferable.

[In the formula (1b), the ring Z ¹ and the ring Z ² each independently represent a substituted or unsubstituted heterocyclic ring.

Y ^1, Y ² and Y ³ are, each independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aryl group having 1 to 8 carbon atoms aliphatic hydrocarbon group or having 6 to 12, ^{Y 1,} Y ^2, and Y ² and Y ^{3 may} combine with each other to form a ring.

u represents an integer of 0 or more and 3 or less.

X ^{b1 -} represents an anion, and b1 represents 1 or 2.

In the formula (1c), ring Z ³ , ring Z ⁴ , ring Z ⁵ And ring Z ⁶ each independently represent a substituted or unsubstituted heterocycle.

A halogen atom, a cyano group, a nitro group, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y ² , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ^8, and Y ⁹ each independently represent a hydrogen atom, And two of Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ and Y ^{9 may} combine with each other to form a ring.

L ¹ represents a substituted or unsubstituted divalent hydrocarbon group of 1 to 16 carbon atoms.

v and w independently represent an integer of 0 or more and 3 or less.

X ^{c1 -} represents an anion, and c 1 represents 1 or 2.

A ring Z ¹ , a ring Z ² , a ring Z ³ , a ring Z ⁴ , a ring Z ⁵ And the ring Z ⁶ include at least one heteroatom as a constituent of the ring and may be monocyclic or polycyclic.

The hetero atom may be an atom selected from the group 15 or 16 element in the periodic table, and examples thereof include a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom and a tellurium atom.

Examples of the heterocycle include an indole ring, a benzoindole ring, an indolenine ring, a benzoindolenine ring, an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzoimidazole ring and a quinoline ring .

Ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ As the substituent which may have a heterocyclic ring represented by Ring Z ⁶ ,

Examples of the alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, An aliphatic hydrocarbon group;

An aryl group having 6 to 12 carbon atoms such as a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o- ;

An aralkyl group having 7 to 10 carbon atoms such as a benzyl group;

An alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy;

An aryloxy group having 6 to 10 carbon atoms such as a phenoxy group;

An aralkyloxy group having 7 to 10 carbon atoms such as a benzyloxy group;

A group having an ester bond such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetoxy group or a benzoyloxy group; a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfamoyl group, a diethylsulfamoyl group, Propylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfamoyl group, di-n-butylsulfamoyl group, 2-ethylhexylsapamoyl group, An alkylsulfamoyl group having 1 to 8 carbon atoms;

An alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

3-en-3-yl group, but-3-en-2-yl group, Pent-4-en-1-yl group and the like;

A nitro group, a cyano group, and the like.

When such a substituent has a hydrogen atom, the hydrogen atom is preferably a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a methoxy group, an ethoxy group, a propoxy group, , Alkoxy groups such as a butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and pentyloxy group, aryloxy groups such as phenoxy group and benzyloxy group, carboxyl group, cyano group, nitro group, acryloyloxy group ; Methacryloyloxy group or the like.

Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by Y ¹ to Y ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, cyclohexyl group and the like.

Examples of the aryl group having 6 to 12 carbon atoms represented by Y ¹ to Y ⁹ include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, , a p-cumene diol group, and a naphthyl group.

Ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ And the ring Z ⁶ is preferably an indole ring, a benzoindole ring, an indolenine ring or a benzoindolenine ring, more preferably an indole ring or an indolenine ring.

Ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ And a heterocyclic ring represented by Z ⁶ is preferably 1 or 2 having an alkyl group or a halogen atom as a substituent.

Y ¹ to Y ³ each independently represent a hydrogen atom, a cyano group, a halogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or two of Y ¹ to Y ³ together form a ring,

Y ¹ to Y ³ each independently represent a hydrogen atom, a cyano group or a halogen atom, more preferably a hydrogen atom.

Y ⁴ to Y ⁹ each independently represent a hydrogen atom, a cyano group, a halogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or two of Y ⁴ to Y ⁹ together form a ring,

Y ⁴ to Y ⁹ each independently represent a hydrogen atom, a cyano group or a halogen atom, more preferably a hydrogen atom.

It is preferable that u, v and w are 1 in terms of brightness of the obtained color filter.

Examples of the divalent hydrocarbon group represented by L ¹ include alkanediyl groups such as methylene, ethylene, ethanediyl, propanediyl, butanediyl, tetramethylene, pentamethylene, and hexamethylene;

A divalent alicyclic hydrocarbon group such as a cyclopentanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, a cyclohexanediyl group and the like;

a divalent aromatic hydrocarbon group such as o-phenylene group, m-phenylene group, p-phenylene group and naphthylene group.

Examples of the substituent which the divalent hydrocarbon group may have include an amino group, a carboxyl group, a cyano group, a nitro group, a halogen atom, and a hydroxy group.

L ¹ represents a ring Z ³ And the ring Z &lt; ⁵ &gt;.

The bivalent hydrocarbon group is preferably an alkanediyl group having 1 to 16 carbon atoms, more preferably an alkanediyl group having 1 to 10 carbon atoms, and still more preferably an alkanediyl group having 3 to 8 carbon atoms.

^Examples of the reverse anion representing X ^{b1 -} or X ^{c1 -} include halide ions, ClO ₄ ^- , OH ^- , organic carboxylic anions, organic sulfonic acid anions, Lewis acid anions, organometallic complex anions, And the like.

Examples of the halide ion include Cl ^- , Br ^- , I ^- and the like.

Examples of the organic carboxylic acid anion include benzoic acid ion, alkanoic acid ion, trihaloalkanoic acid ion, and nicotinic acid ion.

Examples of the organic sulfonic acid anion include a benzenesulfonic acid ion, a naphthalenesulfonic acid ion, a p-toluenesulfonic acid ion, and an alkanesulfonic acid ion.

Examples of Lewis acid anion include BF ₄ ^- , SbF ₆ ^- and the like.

Examples of dye-derived anions include anions derived from an anthraquinone compound derived from a phthalocyanine compound, and anions derived from a phthalocyanine compound.

The organometallic complex anion is composed of a central metal and a ligand. Examples of the ligand include an azo ligand, a bisphenyldithiol ligand, a thiocatecholate ligand, a thiobisphenolate chelate ligand, a bisdiol -Α-diketone ligand and the like. Examples of the central metal include transition metals of Group 3 to Group 11 in the periodic table such as scandium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, Rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, cadmium and mercury.

The ligand is preferably an azo ligand or a bisphenyl dithiol ligand, more preferably an azo ligand.

As the center metal, cobalt, nickel or copper is preferable from the viewpoints of manufacturing cost and easiness of handling.

Specifically, the organometallic complex anion is preferably an azo metal complex anion or a bisphenyl dithiol metal complex anion in which the central metal is cobalt, nickel or copper, and an azo metal whose central metal is cobalt, nickel or copper The metal complex anion is more preferable.

The compound represented by the formula (1b) is preferably the compound represented by the formula (2c).

[In the formula (2c), ring Z ⁷ And ring Z ⁸ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.

^{Y 1 ~ Y 5, u,} X b1- and b1 is the same as in the formula (1b).

Y ¹⁰ And Y ¹¹ each independently represent a monovalent aliphatic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent.

Y ¹² And Y ¹³ each independently represent a hydrogen atom, a halogen atom, or a monovalent aliphatic hydrocarbon group of 1 to 6 carbon atoms which may have a substituent, or monovalent Y ¹² and one Y ¹³ bond to each other to form a carbon number of 2 Lt; 6 &gt; represents a divalent aliphatic hydrocarbon group of 1 to 6 carbon atoms.

and p1 and p2 independently represent an integer of 0 or more and 2 or less.

Examples of the monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, an allyl group, Butyl group, a tert-butyl group, a but-3-en-2-yl group, a buta-1,3-dien-2-yl group, a pentyl group, an isopentyl group, a neopentyl group, A monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a t-butyl group, a 2-methylpentyl group, have.

Examples of the substituent in the monovalent aliphatic hydrocarbon group include a phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, An aromatic hydrocarbon group having 6 to 12 carbon atoms such as cumene diacrylate;

Alkoxy having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, group;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

A hydroxy group, a carboxy group, a nitro group, and a cyano group.

Examples of the divalent aliphatic hydrocarbon group include a methylene group, an ethylene group, a propanediyl group, and a butane diyl group.

Y ¹⁰ And Y ¹¹ each independently represent an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom, and more preferably an alkyl group having 1 to 5 carbon atoms which may be substituted with a halogen atom.

Y ¹² And Y ¹³ each independently represent an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, and more preferably a methyl group or a trifluoromethyl group. Y ¹² And Y ¹³ are preferably the same group.

Examples of the cyanine compound include a compound represented by the formula (2c-1) to a compound represented by the formula (2c-19).

Examples of the cation derived from the cyanine compound include a cation represented by the formula (1b) or a compound represented by the formula (2c).

Examples of salts of cation derived from xanthine compounds and anion derived from cyanine compounds include the salts described below.

The salt content of the xanthene dye and the cyanine dye is usually 0.1 to 20 parts by mass based on 100 parts by mass of the compound (a).

&Lt; Dye (A2) &gt;

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 the range of 580 nm or more and 650 nm or less and more preferably a dye having a maximum absorption wavelength in the range of 600 nm or more and 645 nm or less.

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

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 triarylmethane dye (A4) is a dye containing a compound having a triarylmethane skeleton in its molecule. Examples of the triarylmethane dye (A4) include C.I. acid violet (hereinafter, the description of C.I. acid violet is omitted and only the description of the number is omitted) 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72,

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

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

C. I. Basic Violet 2,

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

C.I. hooded violet 3,

All I. Violet

1, 1, 3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49, etc.

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. Further, 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,

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

C.I. Acid Violet 34,

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

C. I. Disperse Violet 26, 27,

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

C.I. Direct Blue 40,

C.I. All 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 a tautomer thereof.

[In the formula (A7)

g represents an arbitrary natural number.

G ^{g -} represents anion of g.

D represents a heteroaromatic group which may have a substituent.

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

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

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^{7A Examples} of the alkyl group represented by R ^8A include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cycloheptyl group, a cycloheptyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, (Adamantan-1-yl) alkan-1-yl group, a norbornyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, , A methyl norbornyl 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.

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

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A And the group in which -CH ₂ - contained in the alkyl group represented by R ^8A is substituted with -O- includes specifically the following groups. Preferred is a group in which -CH ₂ - contained in an alkyl group having 1 to 10 carbon atoms is substituted with -O-, more preferably -CH ₂ - included in an alkyl group having 1 to 6 carbon atoms is -O- Lt; / RTI &gt;

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

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A And R ^8A each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ^21A And the hydrogen atom contained in the amino group represented by 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, 8 &lt; / RTI &gt;

Examples of the alkyl group which may have a substituent include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- butyl group, pentyl group, hexyl group, A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cycloheptyl group, a cycloheptyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, A cyclohexyl group, a cyclodecyl group, a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan- A norbornyl group, a methylnorbornyl group and an isobornyl group. Other than the -CH ₂ - - -CH ₂ adjacent to the nitrogen atom contained in the alkyl group is optionally substituted by -O-, with substituents which may have the alkyl group has is an amino group, substituted amino group, a halogen atom and a silicon And a group containing an atom.

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 a methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, sec-butylamino group, tert-butylamino group, dimethylamino group, diethylamino group, dipropylamino group, An alkylamino group having 1 to 8 carbon atoms 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 from 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), R ^15A represents an acryloyl group or a methacryloyl group.

R ^14A represents an alkanediyl group having 1 to 8 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -O-.

* Represents the bond with the nitrogen atom.]

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

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

R ^{21A Examples} of the optionally substituted amino group represented by R ^22A include a methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, tert- , A methylamino group, an ethylamino group, an ethylamino group, an ethylamino group, an isopropylamino group, an isopropylamino group, a methylpropylamino group, a phenylamino group, N-methylphenylamino group, acryloyloxymethylamino group, N-methylphenylamino group, 3-methylphenylamino group, 3-methylphenylamino group, 3,5-dimethylphenylamino group, - (acryloyloxymethyl) -N-methyl Amino group, N- (acryloyloxyethyl) -N-ethylamino group, N- (methacryloyloxyethyl) -N-ethylamino group, N- (acryloyloxyethyl) (Acryloyloxyethyl) -N- (methacryloyloxymethyl) 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 pyridyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzothiazolyl , 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, An aryl group is preferred.

As the amino group which may be substituted, R ^21A And an amino group which may be substituted and represented by 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. 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 the carbon atom.]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ include R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A And the alkyl group having 1 to 20 carbon atoms represented by R &lt; ^8A &gt;.

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

As the optionally substituted amino group represented by R ⁵⁶ , R ^21A And an amino group which may be substituted and represented by 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 optionally substituted amino group.

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 anion, formula (y2) is represented by a monovalent anion which is preferred, for example, a fluoride ion, chloride ion, bromide ion, and halide ions such as iodide ions, 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 formula (y2), R ^B2 And R ^B3 are each independently represented by a halogen atom or a halogenated hydrocarbon group, or R ^B2 and R ^B3 are engaged with each other -SO ₂ -N ^- to form a ring containing a - -SO _2.

In the formula (y3), M represents an aluminum atom or a boron atom, ^{R 4} and R ^B is ^B5, each independently represents 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 acyl group, 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, Perfluoroethylmethyl group, a 1- (trifluoromethyl) benzyl group, a trifluoromethyl group, a trifluoromethyl group, a trifluoromethyl group, Tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl A perfluorobutyl group, a dibromomethyl group, and a tribromomethyl group, preferably an alkyl group having 1 to 20 carbon atoms, 8 fluorinated alkyl group.

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

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.

R ^B2 The halogen atom represented by R ^B3 includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or a chlorine atom.

R ^B2 And halogenated hydrocarbon groups represented by 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, Perfluoroethylmethyl group, a 1- (trifluoromethyl) benzyl group, a trifluoromethyl group, a trifluoromethyl group, a trifluoromethyl group, Tetrafluoroethyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl A perfluorobutyl group, a dibromomethyl group, and a tribromomethyl group, preferably an alkyl group having 1 to 20 carbon atoms, 8 fluorinated alkyl group.

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

R ^B2 And R ^B3 are preferably the same group.

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

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

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

Examples of the anion represented by formula (y1) include methanesulfonate anion, toluenesulfonate anion, dodecylbenzenesulfonate anion, trifluoromethanesulfonate anion, perfluorobutanesulfonate anion, phenylsulfonate anion, And fluorophenylsulfonic acid anion.

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

The anion represented by the formula (y3) includes the anion 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) is 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 a structural unit derived from a blue or purple dye and may be a polymer consisting only of a structural unit derived from a blue or purple dye and may be a polymer different from a structural unit derived from a blue or purple dye (Hereinafter may be referred to as copolymer (a) in some cases). The structural unit derived from the blue or purple dye may be a divalent or higher donor generated by polymerization of a polymerizable blue or purple dye and may be a monovalent or higher donor consisting of a blue or purple dye excluding one or more hydrogen atoms. Examples of the copolymer (a) include, in addition to the structural unit derived from the blue or violet 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.

The copolymer (a) may also be a copolymer comprising a structural unit derived from a monomer for introducing a 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, an alkylaryl group which may have a substituent, .

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 &lt; ¹³ &gt; 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, an alkylaryl group which may have a substituent, .

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, R ¹⁵ And R &lt; ¹⁶ &gt; are bonded to each other to form a ring.

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

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

Further, it may contain a structural unit derived from a monomer capable of copolymerizing with a structural unit derived from a monomer having an ethylenic unsaturated bond, and specific examples thereof include alkenyl such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl methyl ether Aromatic monomers;

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-dimethyl amino ethyl acrylate and 2-dimethyl amino ethyl 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) At least one kind is preferable.

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

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

Further, the blue or violet dye and the compound (a) may form a salt. Examples of the salt composed of the blue or purple dye and the compound (a) include a salt composed of a cation derived from a blue or purple dye and an anion derived from the compound (a).

Examples of the salt comprising the blue or purple dye and the compound (a) include those described below.

The content of the dye (A2) is usually from 80 to 10,000 parts by mass, preferably from 80 to 7,000 parts by mass, more preferably from 80 to 1,000 parts by mass, and still more preferably from 80 to 10,000 parts by mass based on 100 parts by mass of the xanthene dye Is 80 to 600 parts by mass.

&Lt; Dye (Ac) and Pigment (A1) &gt;

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

The pigment (A1) is not particularly limited and a known pigment can be used, and for example, a pigment classified in pigment in the color index (The Society of Dyers and Colourists) is cited.

Examples of the pigment include blue pigments such as C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6 and 60,

Violet pigments such as CI 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) Compound (a), CI Acid Red 52 and blue or purple dye (A2)

(2) Compound (a), C.I. acid red 52, blue or purple dye (A2) and blue pigment

(3) Compound (a), C.I. Acid Red 52, blue or purple dye (A2) and violet pigment

(4) Compound (a), C.I. Acid Red 52, blue or purple dye (A2), blue pigment and violet pigment

The content of the colorant (A) is preferably from 5 to 60 mass%, more preferably from 8 to 55 mass%, and still more preferably from 10 to 50 mass%, based on the total solid content.

When the content of the colorant (A) is within the above range, the color density of the color filter is sufficient and the resin (B) or the polymerizable compound (C) can be contained in a required amount in the composition. A sufficient pattern can be formed. Here, the "total amount of solid content" in the present specification means the amount obtained by subtracting 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.

&Lt; Resin (B) &gt;

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 may be 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 and an ethylenic unsaturated bond (Hereinafter may be referred to as &quot; (b) &quot;);

(Hereinafter referred to as &quot; (c) &quot;), which is copolymerizable with the resin (K2) (a) and (b) );

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] A resin obtained by reacting the copolymer of (b) and (c) with (a) and reacting with a carboxylic acid anhydride.

(a) specifically 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 dimethyl tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

2,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] logistics;

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;

Unsaturated mono [(meth) acryloyloxyalkyl] ester of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Ryu;

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 (e.g., oxirane ring. An oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (B) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, the term "(meth) acrylic acid" refers to at least one member 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, a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (Hereinafter may be 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) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, an alicyclic (B1-2) having a structure in which unsaturated hydrocarbons are 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- (Glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) steel 2,4,6-tris (glycidyloxymethyl) styrene, and the like.

(B1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; Daicel), 3,4-epoxycyclohexylmethyl Acrylate (for example, cyclomer A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., , A compound represented by the formula (I) and a compound represented by the formula (II).

[In the formulas (I) 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 -O-, * -R ^c -S- or * -R ^c -NH-.

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

* Indicates a binding hand with O.]

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

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, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be given .

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

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- And a 1,6-diyl group.

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- (* represents a bond with O).

Examples of the compound represented by the formula (I) include a compound represented by the formula (I-1) to a compound represented by the formula (I-15). Preferably, the compound represented by formula (I-1), the compound represented by formula (I-3), the compound represented by formula (I-5), the compound represented by formula (I- -9) or a compound represented by the formula (I-11) to a compound represented by the formula (I-15). More preferably, the compound represented by formula (I-1), the compound represented by formula (I-7), the compound represented by formula (I-9) have.

Examples of the compound represented by the formula (II) include a compound represented by the formula (II-1) to a compound represented by the formula (II-15). Preferably, the compound represented by formula (II-1), the compound represented by formula (II-3), the compound represented by formula (II-5), the compound represented by formula (II- -9) or a compound represented by the formula (II-11) to a compound represented by the formula (II-15). More preferably, the compound represented by formula (II-1), the compound represented by formula (II-7), the compound represented by formula (II-9) or the formula (II-15)

The compound represented by formula (I) and the compound represented by formula (II) may be used alone. In addition, they can be mixed at an arbitrary ratio. (II), preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20: : 80 to 80:20.

(B2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl- 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 reliability of the resulting color filter can be further improved, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable because the storage stability of the colored curable resin composition can be obtained.

(Meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (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 (in the art, Quot; acrylate &quot; (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, (Meth) acrylates such as propyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

2-hydroxyethyl (meth) acrylate,

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

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

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'- 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept- , 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- 2,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-di -Diethoxybicyclo [2.2.1] hept-2-ene, 5-hydro Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [ 2.1] hept-2-ene, and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, Dicarbonylimide derivatives such as 6-maleimidocaproic acid, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

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] hept-2- ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance .

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

(A); 2 to 60 mol%

(B) is preferably 40 to 98% by mole,

(A) in an amount of 10 to 50 mol%

More preferably 50 to 90 mol% of a structural unit derived from the structural unit (b).

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

Resin [K1] can be synthesized by, for example, the method described in "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, . The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the field can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), organic peroxides (such as benzoyl peroxide And the solvent may be any solvent as long as it dissolves the respective monomers. As the solvent (E) of the colored curable resin composition of the present invention, there may be mentioned a solvent to be described later.

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. Particularly, by using the solvent contained in the colored photosensitive 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 photosensitive resin composition of the present invention. Therefore, the colored photosensitive resin composition Can be simplified.

In the resin [K2], the ratio of the structural units derived from each other is preferably such that, among all structural units constituting the resin [K2]

(A); 2 to 45 mol%

(B); 2 to 95 mol%

(C) is preferably from 1 to 65% by mole,

(A); 5 to 40 mol%

(B); 5 to 80 mol%

More preferably 5 to 60 mol% of a structural unit derived from the structural unit (c).

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, developability in forming a colored pattern, and solvent resistance, heat resistance and mechanical strength of the obtained color filter tend to be excellent .

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 resin [K3]

(A); 2 to 60 mol%

(C) is preferably 40 to 98% by mole,

(A) in an amount of 10 to 50 mol%

More preferably 50 to 90 mol% of a structural unit derived from the structural unit (c).

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

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

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

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

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 a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris ) Phenol, etc.) and a polymerization inhibitor (such as hydroquinone) are placed in a flask and reacted at 60 to 130 ° C for 1 to 10 hours, for example.

(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 preferable and (b1-1) is preferable for (b) used for the resin [K4] because the reactivity of the cyclic ether is high and the unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass based on 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 charging 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. In addition, as in the case of the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facilities 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 method of resin [K1]. In the same way as the above, the solution obtained after the reaction may be used as it is, or a solution obtained by concentrating or diluting 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) is preferably such that the total number of moles of the structural units constituting the above-

(B); 5 to 95 mol%

(C) is preferably from 5 to 95 mol%, more preferably from 5 to 95 mol%

(B); 10 to 90 mol%

(C) is 10 to 90 mol%.

The carboxylic acid or carboxylic acid anhydride of (a) is reacted with the cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as in the production of resin [K4] [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 preferable and (b1-1) is preferable for (b) used for the resin [K5] because the reactivity of the cyclic ether is high and the unreacted (b)

Resin [K6] is a resin obtained by reacting a resin [K5] with a carboxylic acid anhydride.

A carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of a cyclic ether and a carboxylic acid or a carboxylic 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 (humic acid 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 (Meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, (Meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymers, styrene / (meth) Resin [K3] is a resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding a tricyclodecyl (meth) acrylate / styrene / (meth) (Meth) acrylate, and a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / Resin [K4] is a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (K5) such as a resin obtained by reacting a copolymer of (meth) acrylate with (meth) acrylic acid, such as tricyclodecyl (meth) acrylate / Sidil (meth) to the resin by reacting the (meth) acrylic acid in the copolymer of the acrylate may also be a resin [K6] such as resin or the like reacted with tetrahydrophthalic anhydride.

Among them, resin (K) and resin (K2) are preferable as resin (B).

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 to 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, and still more preferably 70 to 135 mg-KOH / g. Here, 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 from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total solid content.

&Lt; Polymerizable compound (C) &gt;

The polymerizable compound (C) is a compound capable of being polymerized by an active radical and / or an acid generated from the polymerization initiator (D), for example, 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 polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, pentaerythritol hexa (meth) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (metha) acrylate, tetrapentaerythritol deca (Meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (metha) ) Acrylate, propylene glycol Caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (metha) acrylate.

Among them, 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 still more 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 the coloring pattern and the chemical resistance of the color filter tend to be improved.

&Lt; Polymerization initiator (D) &gt;

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. 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-acyloxime compounds and imidazole compounds is preferable, and O -Acyloxime compound is more preferable.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane- 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N- acetoxy-1- [9- Benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) - 9H-carbazol- H- carbazole-3-yl; and the like can be mentioned 3-cyclopentyl-1-circle-2-imine. Commercially available products such as Sigma-Cure OXE01, OXE02 (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- -One-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine is more preferable. If these O-acyloxime compounds are used, color filters of high brightness tend to be obtained.

The alkylphenone compound is preferably a 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propane- -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2- 1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- (2- hydroxyethoxy) phenyl] Oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one, α, α-diethoxyacetophenone and benzyl dimethyl ketal. (Commercially available from BASF Co., Ltd.) may be used.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran- (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- 6- [2- (3,4- Dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis -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 Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Application Laid- 3, No. 62-174204, etc.), imidazole compounds in which the phenyl group at the 4,4'5,5'-position is substituted by a carboalkoxy group (for example, Japanese Patent Application Laid-Open No. 7-10913, etc.).

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, Benzophenone such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, and 2,4,6- Phenol compounds, quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone and camphorquinone, 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds have. These are preferably used in combination with the polymerization initiator D1 (particularly amines) described below.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfate Triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Phenyl iodonium hexafluoroantimonate and the like, nitrobenzyl tosylates, benzoin tosylates and the like.

The content of the polymerization initiator (D) 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) . When the content of the polymerization initiator (D) is within the above range, the sensitivity is improved and the exposure time is shortened, so that the productivity of the color filter is improved.

&Lt; Polymerization initiator (D1) &gt;

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, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, (Diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone (commonly referred to as Mihirazuketone), 4,4'- , 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry 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, Dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- Citoxanthone 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, its content is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 30 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) 20 parts by mass. When the amount of the polymerization initiator (D1) is within this range, a colored pattern can be formed with high sensitivity, and the productivity of the color filter tends to be improved.

&Lt; Solvent (E) &gt;

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -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 including -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, methyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, , Butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetone 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 glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 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, A brush, 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, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, 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, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether And the like can be given three lactate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.

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

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

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

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetoamide 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. Examples of the solvent include 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 in the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density tends not to be insufficient when the color filter is formed, so that display characteristics tend to be good.

&Lt; Leveling agent (F) &gt;

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. Concretely, Toray Silicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH8400 (trade name: TORAY DOUING CO., LTD.), KP321, KP322, KP323, KP324, KP340, KP341 (manufactured by Shinko Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan Cooperation Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, there are used ProRad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megafox (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554, R30, RS-718-K (manufactured by DIC Corporation), S-top® EF301, S-EF303, S-EF351 and EF352 (manufactured by Mitsubishi Materials Electronics Co., , S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.).

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

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, based on the total amount of the tin curable resin composition , More preferably 0.01 mass% 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.

&Lt; Process for producing colored curable resin composition &gt;

The colored curable resin composition of the present invention can be obtained, for example, by mixing 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 the dye (Ac) to be used as needed may be dissolved in a part or all of the solvent (E) beforehand to prepare a solution. The solution is preferably filtered with a filter having a pore diameter of about 0.01 to 1 mu m.

The blue pigment (A1) is preferably mixed with part or all of the solvent (E) and dispersed with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, if necessary, a part or all 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 diameter 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. The 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 newspaper, etc.) and a solid-state image pickup device.

[Mode for Carrying Out the Invention]

[Example]

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by examples.

In the examples, &quot;% &quot; and &quot; part &quot; 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 label analysis (VARIO-EL;

[Synthesis Example 1]

To the reactor, 32.3 parts of para-rosaniline hydrochloride (manufactured by TOKYO CHEMICAL CO., LTD.) Was added to 500 parts of anhydrous ethanol, refluxed for 8 hours, and cooled to room temperature. To the obtained mixture, 20.2 parts of the compound represented by the formula (a2-1) was slowly added dropwise over 5 hours. After the dropwise addition, the resulting mixture was stirred at 70 캜 for 36 hours and then cooled to room temperature to obtain 48.8 parts of a compound represented by the formula (a2).

[Synthesis Example 2]

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 mixture was heated to 40 占 폚 and held. After the completion of the reaction, the reaction mixture was cooled to room temperature, water was added thereto, layered, and 20 mL of saturated brine was further added, followed by stirring for 30 minutes. After layer decomposition, the organic layer was distilled and evaporated, 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. Thereafter, 49.08 parts of phosphorus oxychloride was further added and the mixture was 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 decompose the layers. The organic layer was distilled and evaporated, and the remaining solid was dried under reduced pressure to obtain 20.3 parts of a compound represented by the formula (aa3).

[Synthesis Example 3]

10.00 parts of the compound represented by the formula (aa3) was added to 100 mL of methanol and dissolved, and then 2.09 parts of lithium bistrifluoromethanesulfonimide was added to replace the salt. After filtration, the resulting 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 4-7]

Benzyl methacrylate, methacrylic acid, methyl methacrylate and N-benzyl maleimide represented by the formula (aa5) were put into a flask equipped with a cooling tube and a stirrer at the weight ratios shown in Table 1 below, and 2 , 2'-azobis (2,4-dimethylvaleronitrile) (initiator) was added in an amount of 6 parts by weight based on 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 in an atmosphere of nitrogen. The reaction solution was heated to 90 DEG C and stirred for 10 hours to obtain a copolymer solution.

[Table 1]

[Synthesis Example 8]

The following reaction was carried out in a nitrogen atmosphere. 36.3 parts of potassium thiocyanate and 160.0 parts of acetone were added to a flask equipped with a condenser and a cooling tube and stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of benzoic acid chloride (manufactured by TOKYO CHEMICAL CO., LTD.) Was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Then, after the reaction mixture was ice-cooled, 45.7 parts of N-ethyl-o-toluidine (manufactured by TOKYO CHEMICAL Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was stirred again at room temperature for 30 minutes. Subsequently, the reaction mixture was ice-cooled, and 34.2 parts of a 30% aqueous solution of sodium hydroxide was added dropwise. After completion of the dropwise addition, the mixture was stirred again at room temperature for 30 minutes.

Subsequently, 35.3 parts of chloroacetic acid at room temperature was added dropwise. After completion of the dropwise addition, the mixture was stirred for 7 hours under reflux. Subsequently, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, and 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 normal hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of gum 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 evaporated with a solvent 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 under reduced pressure at 60 캜 to obtain 52.0 parts of a compound represented by the formula (B-I-1).

Yield 50%

[Synthesis Example 9]

The following reaction was carried out in a nitrogen atmosphere. 9.3 parts of a compound represented by the formula (B-I-1), 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) And 20.0 parts of toluene were added. Then, 14.8 parts of phosphorus oxychloride was added, 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 saline, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Subsequently, stirring was stopped, and the mixture was allowed to stand for 30 minutes. 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, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated by evaporation with an evaporator to obtain a bluish green solid. Further, the violet solid was dried under reduced pressure at 60 캜 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

[Synthesis Example 10]

The following reaction was carried out in a nitrogen atmosphere. 10.0 parts of a compound represented by the formula (A-I-a1), 4 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Kasei Kogyo Co., Ltd.) , And N, N-dimethylformamide (100.0 parts) were charged, 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 cyan-blue solid. The blue-green solid was further dried at 60 DEG C under reduced pressure to obtain 11.3 parts of a compound represented by the formula (A-I-a9).

Yield 82%

[Synthesis Example 11]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 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 34 parts by mass of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by the formula (I-1) Compound at a molar ratio of 50:50) was dissolved in 185 parts by mass of ethyl lactate to prepare a solution. The solution was kept at 70 ° C for 4 hours using a dropping funnel Was added dropwise to the flask.

On the other hand, a solution obtained by dissolving 30 parts by weight of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by weight 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 maintained 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, %, And a solid acid value of 120 mg-KOH / g. Resin B1 has the following structural unit.

[Synthesis Example 12]

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-introducing tube, the atmosphere in the flask was changed from nitrogen to nitrogen, A mixture composed of 70.5 parts of acrylate, 43.0 parts of methacrylic acid, 22.0 parts of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 parts of propylene glycol monomethyl ether acetate And 3.6 parts of 2,2'-azobisisobutyronitrile was added dropwise, and stirring was further continued at 100 ° C.

Next, the atmosphere in the flask was purged with nitrogen from air, and 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)], trisdimethylamino 0.9 part of methylphenol and 0.145 part of hydroquinone were charged into a flask and the reaction was continued at 110 DEG C to obtain a resin B2 solution having a solid content of 29% and a solid acid value 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 (Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 占 폚

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0 mL / min

Detector; RI

TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500 and 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 13]

Synthesis was conducted in the same manner as in Synthesis Example 6 except that the compound represented by the formula (B-I-1) was used instead of the N-phenyl-1-naphthylamine in Synthesis Example 2 to obtain the compound represented by the formula (aa13) &Lt; / RTI &gt;

[Synthesis Example 14-17]

A copolymer solution was obtained in the same manner as in Synthesis Example 4-7, except that the monomer represented by the formula (aa13) was used instead of the monomer represented by the formula (aa5).

[Table 2]

[Synthesis Example 18]

22.14 parts of disodium 4-formylbenzene-1,3-disulfonate, 15.6 parts of N, N-dibutyl-3-aminophenol and 2.2 parts of sodium para-toluenesulfonate were stirred at 120 ° C for 12 hours did. After cooling, the resulting mixture was added to 100 parts of 50% water in ethanol and filtered to obtain a compound represented by the formula (I-2).

[Synthesis Example 19]

10.00 parts of the compound represented by 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 20]

30 parts of methyl ethyl ketone was added in a nitrogen atmosphere, and then the temperature was raised to 70 占 폚. 2.54 parts of a 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 to partially concentrate methyl ethyl ketone. The reaction solution was then added to hexane to precipitate crystals, which were then filtered, washed with hexane and dried under reduced pressure To obtain 1.80 parts of a polymer compound (aa4).

[Synthesis Example 21]

30 parts of methyl ethyl ketone was added in a nitrogen atmosphere, and then 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, 0.42 part was dissolved in 50 parts of methyl ethyl ketone, and the mixture was kept at 70 캜 for 3 hours. After completion of the addition, the mixture was maintained at 70 DEG C for 8 hours to partially concentrate methyl ethyl ketone. The reaction solution was then added to hexane to precipitate crystals, which were then filtered, washed with hexane and dried under reduced pressure To obtain 2.35 parts of a polymer compound (aa4 ').

[Synthesis Example 22]

30 parts of methyl ethyl ketone was added in a nitrogen atmosphere, and then 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 kept at 70 ° C for 3 hours. After completion of the addition, the mixture was maintained at 70 ° C for 8 hours to partially concentrate methyl ethyl ketone. The reaction solution was then added to hexane to precipitate crystals. The crystals were collected by filtration, washed with hexane and dried under reduced pressure To obtain 1.63 parts of a polymer compound (aa5).

[Synthesis Example 23]

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 a compound represented by the formula (aa5), 0.25 part of 2,2'-azobisisobutyronitrile, 0.51 part of benzyl methacrylate, and 0.51 part of methacrylic acid. 0.42 part of N-phenylmaleimide was 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 reaction mixture was maintained at 70 DEG C for 15 hours to partially concentrate methyl ethyl ketone. The reaction solution was then added to hexane, and the crystals were precipitated and filtered, and the remaining solid was dried under reduced pressure to obtain a polymer compound (aa5 ' ).

[Synthesis Example 24]

5.00 parts of the compound represented by the formula (aa3) was added to 50 mL of methanol and dissolved, and 1.46 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 2.84 parts of a compound represented by the formula (aa6).

[Synthesis Example 25]

5.00 parts of C. I. Basic Blue 26 were dissolved by adding 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 26-29]

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 3, respectively, 0.25 parts of 2,2'-azobisisobutyronitrile as an initiator, and 6 parts by weight of benzyl methacrylate were added to 100 parts by weight of the total amount of the monomers. Subsequently, 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was added to 100 parts by weight of the total amount of the initiator and the monomer, and then stirring was started slowly in a nitrogen atmosphere. The reaction solution is heated to 90 DEG C and stirred for 10 hours to obtain a copolymer solution.

[Table 3]

[Synthesis Example 30-33]

A copolymer solution was obtained in the same manner as in Synthesis Examples 26-29, except that the monomer represented by the formula (aa9) was used instead of the monomer represented by the formula (aa8).

[Table 4]

[Synthesis Examples 34-37]

A copolymer solution was obtained in the same manner as in Synthesis Examples 26-29, except that the monomer represented by the formula (aa10) was used instead of the monomer represented by the formula (aa8).

[Table 5]

[Synthesis Example 38]

2.1 parts of Basic Blue 7 (Tokyo Chemical Industry Co., Ltd.) was dissolved in 100 parts of methanol and then 2.1 parts of a compound represented by the following formula (Pc) (manufactured by Aldrich) Lt; / RTI &gt; Thereafter, 100 parts of ion-exchanged water was added to precipitate crystals. After filtration, the crystals were washed with 50 parts of ion-exchanged water, and the obtained solid was dried at 60 DEG C for 24 hours to obtain a compound represented by the formula (a-4).

[Example 1]

(Preparation of colored curable resin composition)

(A) Colorant: 10 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 1.0 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator: 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 2]

(Preparation of colored curable resin composition)

(A) Colorant: 10 parts of a compound represented by the formula (a-1)

(A) Colorant: 1.0 part of a compound represented by the formula (I-2)

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 3]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.5 part

(A) Colorant: 6.0 parts of a compound represented by the formula (a2)

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator: 10 parts of N-benzoyloxy- 1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Ilgacure (registered trademark) OXE 01, manufactured by BASF)

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 4]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: 0.5 part of a compound represented by the formula (I-2)

(A) Colorant: Compound represented by the formula (a2) 5.8 parts

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 5]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.5 part

(A) Colorant (A5): 0.5 part of a compound represented by the formula (2-29)

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, manufactured by BASF)

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 6]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.5 part

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 7]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant (A7): 5.0 parts of a compound represented by the formula (A-I-a9)

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 8]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthetic Example 4

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 9]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 5

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, manufactured by BASF)

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 10]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 6

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 11]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 7

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 12]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 14

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, manufactured by BASF)

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 13]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 15

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

(F) Leveling agent: polyether-modified silicone oil

SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 14]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 16

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 15]

(Preparation of colored curable resin composition)

(A) Colorant: 2.0 parts of a compound represented by the formula (a-1)

(A) Colorant: CI Acid Red 52 0.3 part

(A) Colorant: 5.0 parts of the copolymer solution obtained in Synthesis Example 17

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 16]

(Preparation of colored curable resin composition)

(A) Colorant: 0.8 part of a compound represented by the formula (a-4)

(A) Colorant: CI Acid Red 52 0.3 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Example 17]

(Preparation of colored curable resin composition)

Except that the compound represented by the formula (aa4) obtained in the synthesis example 7 was used in place of the compound represented by the formula

To obtain a composition.

[Example 18]

(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 (aa5) obtained in Synthesis Example 8 was used instead of the xanthene dye.

[Example 19]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the polymer compound (aa4 ') obtained in Synthesis Example 21 was used instead of the compound represented by the formula (a2).

[Example 20]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the polymer compound (aa5) obtained in Synthesis Example 22 was used instead of the compound represented by Formula (a2).

[Example 21]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the polymer compound (aa5 ') obtained in Synthesis Example 23 was used instead of the compound represented by the formula (a2).

[Example 22]

(Preparation of colored curable resin composition)

A colored curable resin composition is obtained in the same manner as in Example 3, except that the polymer compound (aa6) obtained in Synthesis Example 24 is used instead of the compound represented by Formula (a2).

[Example 23]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3 except that the polymer compound (aa7) obtained in Synthesis Example 25 was used instead of the compound represented by the formula (a2).

[Example 24]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 26 was used in place of the compound represented by the formula (a2).

[Example 25]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 27 was used instead of the compound represented by the formula (a2).

[Example 26]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 28 was used in place of the compound represented by the formula (a2).

[Example 27]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 29 was used in place of the compound represented by the formula (a2).

[Example 28]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 30 was used in place of the compound represented by the formula (a2).

[Example 29]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 31 was used in place of the compound represented by the formula (a2).

[Example 30]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 32 was used in place of the compound represented by the formula (a2).

[Example 31]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 33 was used in place of the compound represented by the formula (a2).

[Example 32]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 34 was used in place of the compound represented by the formula (a2).

[Example 33]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 35 was used in place of the compound represented by the formula (a2).

[Example 34]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 36 was used in place of the compound represented by the formula (a2).

[Example 35]

(Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the copolymer dispersion obtained in Synthesis Example 37 was used in place of the compound represented by the formula (a2).

[Example 38]

(Preparation of colored curable resin composition)

Except that the compound represented by the formula (4-9) was used in place of the compound represented by the formula (a2), and further the colorant CI Pigment Violet 23 was contained, the coloring curability To obtain a resin composition.

[Example 39]

(Preparation of colored curable resin composition)

Except that the compound represented by the formula (1-44) was used in place of the compound represented by the formula (a2), and further the colorant contained C.I. Pigment Violet 23, the coloring curability To obtain a resin composition.

[Comparative Example 1]

(Preparation of colored curable resin composition)

(A) Colorant: 10 parts of a compound represented by the formula (a-1)

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 600 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

[Comparative Example 2]

(Preparation of colored curable resin composition)

(A) Colorant: 0.8 part of a compound represented by the formula (a-4)

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) Polymerization initiator 10 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (IGACURE (registered trademark) OXE 01,

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

(E) Solvent: ethyl lactate 550 parts

(E) Solvent: Propylene glycol monomethyl ether acetate 10 parts

Were mixed to obtain a colored curable resin composition.

&Lt; Fabrication of coloring pattern &

The colored curable resin composition was applied to a 5 cm-corrugated glass substrate (Eagle 2000; Corning) by spin coating, and then pre-baked at 100 ° C for 3 minutes to obtain a colored layer.

After cooling down, an exposure amount (365 nm) of 150 mJ / cm ² was measured under an atmospheric environment using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an interval of 100 mu m between the substrate on which the colored layer was formed and the quartz glass photomask Standard). 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 transferred to a post in an oven at 200 DEG C for 30 minutes Baking was carried out to obtain a colored pattern.

&Lt; 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 Japan Vacuum Technology Co., Ltd.)).

&Lt; Evaluation of color &

The spectroscopic measurement was performed using a colorimeter (OSP-SP-200; manufactured by Orissa Co., Ltd.) with respect to the obtained color pattern, and the xy chromaticity coordinates (x, y) of the CIE XYZ color system, y) and three stimulus values Y were measured. The larger the value of Y, the higher the brightness.

[Heat resistance evaluation]

The coated film of the obtained colored photosensitive resin composition was heated at 230 占 폚 for 20 minutes and the color difference? Eab * before and after heating of the coated film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The obtained coating film was subjected to the above heat resistance evaluation, and as a result, the color difference ([Delta] Eab *) is shown in Tables 6 to 9. The smaller the? Eab *, the smaller the color change before and after heating, and the better the heat resistance.

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Industrial applicability]

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

Claims (3)

A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D)
Wherein the colorant (A) comprises a compound represented by the formula (a)
At least one selected from the group consisting of xanthene dyes and salts of xanthene dyes and cyanine dyes,
Wherein the xanthene dye is a compound represented by CI Acid 52 or the following formula (I).

Wherein k1, k2, k3 and k4 independently represent an integer of 0 to 4, and 4? K1 + k2 + k3 + k4? 16.
X _a ^- , X _b ^- , X _c ^- and X _d ^- each independently represent -CO ₃ ^- or -SO ₃ ^- .
A _a ⁺ , A _b ⁺ , A _c ⁺ and A _d ⁺ each independently represent a sodium ion, a potassium ion or a cation represented by the formula (b).

In formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² and R ¹⁰³ independently represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.

[In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 2 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent.
R ^51, R ⁵² and R ⁵³ are, each independently, a hydrogen atom, -SO ₃ ^- represents a ⁺ Z ^-, -SO ₃ H or -SO _3.
X ^&lt; ⁺ &gt; represents Na ^{& lt} ; ^{+ &} gt ^; or K ⁺
Z ⁺ represents a N ^{+ (R} _{13) 4,} Na ⁺ or K ^+,
R ¹³ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. R ¹³ may be the same or different. a represents an integer of 1 to 4.]
delete The method according to claim 1 or 2,
, Wherein the colorant (A) further comprises a blue or violet dye (A2).