TWI679494B - Colored curable resin composition - Google Patents

Abstract

An object of the present invention is to provide a color filter having good heat resistance and brightness.

A colored curable resin composition containing a colorant (A), a resin (B), The polymerizable compound (C) and the polymerization initiator (D), wherein the colorant (A) includes a compound represented by the formula (a), and is selected from the group consisting of a dibenzopiran (xanthene) dye and a dibenzopiper At least one of the group consisting of a cyan dye and a salt of an anthocyanin dye.

[Wherein, k1, k2, k3 and k4 based independently of each 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 lines and -CO ₃ ^- or ^{_{-SO 3 -; A a +,}} A b +, A c + A _d ⁺ line and each independently represents a cation and a sodium ion, a potassium ion, or of formula (b), of; In formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ^102, and R ¹⁰³ are each independently and represent a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms].

Description

Colored curable resin composition Field of invention

The present invention relates to a colored curable resin composition.

Background of the invention

A color filter formed of a coloring curable resin composition is required to be used in a display device such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel, and has good brightness, good contrast, Color filter with good resolution.

In order to realize a color filter with good brightness, good contrast, and good resolution, a color-hardening resin composition containing a dye as a colorant is currently under discussion, but due to the dye, heat resistance, chemical resistance, etc. The decline has become a problem.

Patent Document 1 describes a coloring curable resin composition containing CI Pigment Blue 15: 6 as a colorant, CI Acid Red 52 and a dye represented by the following formula, and 100 parts by mass of CI Pigment Blue 15 : 6, The content of CI Acid Red 52 is 14.7 parts by mass.

Advance technical literature Patent literature

Patent Document 1: Japanese Patent Application Publication No. 2013-144724.

Summary of invention

The color filter formed of the coloring curable resin composition does not necessarily satisfy both of heat resistance and brightness.

The present invention includes the following inventions.

[1] A colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) includes: And a compound selected from the group consisting of a xanthene dye and a salt of a dibenzopiperan dye and an anthocyanin dye.

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

_{^{X a -, X b -,}} X c - and X _d ^- based and 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 formula (b).

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

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

[In 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 independently of each line represent 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.

a represents an integer of 1 to 4. A

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

Detailed description of the preferred embodiment Forms used to implement the invention

The colored curable resin composition of the present invention includes 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 the group consisting of a solvent (E) and a leveling agent (F).

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

<Colorant (A)>

The colorant (A) contains a compound represented by the formula (a) (hereinafter, also referred to as a compound (a)), and is selected from the group consisting of a dibenzopiperan dye, a dibenzopiperan dye, and an anthocyanin dye. At least one of the groups consisting of salt.

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

Moreover, in this application, "C.I." means a color index.

<Compound (a)>

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

_{^{X a -, X b -,}} X c - and X _d ^- based and 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 formula (b).

In formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ^102, and R ¹⁰³ are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a heterocyclic group having 6 to 30 carbon atoms. A

k1, k2, k3, and k4 are independent and represent integers of 0 to 4. However, 1 ≦ k1 + k2 + k3 + k4 ≦ 16, and preferably 1 ≦ k1 + k2 + k3 + k4 ≦ 2.

Examples of the hydrocarbon group represented by R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² and R ¹⁰³ include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n-nonyl. , N-decyl, n-dodecyl, n-hexadecyl and n-icosyl, etc. linear alkyl groups having 1 to 30 carbon atoms; isopropyl, isobutyl, secondary butyl, tertiary butyl, Isopentyl, neopentyl, 2-ethylhexyl and other branched alkyl groups having 3 to 30 carbon atoms; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl Alicyclic saturated hydrocarbon group having 3 to 30 carbon atoms. An alkyl group having 1 to 8 carbon atoms is preferred, and an alkyl group having 1 to 4 carbon atoms is preferred.

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

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

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

<Dibenzopiperan dye>

A dibenzopiperan dye means a dye containing a compound having a dibenzopiperan skeleton. The dibenzopiperan dye is preferably a dibenzopiperan dye having 2 -SO ₃ ^- groups as a substituent, and CI Acid Red 52 and its derivatives are preferred. The class of CI Acid Red 52 is a compound (hereinafter, also referred to as compound (I)) represented by formula (I).

<Compound (I)>

[In 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 independently of each line represent 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.

a represents an integer of 1 to 4. A

R ¹ , R ² , R ³ and R ^{4 are} monovalent saturated hydrocarbon groups having 2 to 10 carbon atoms, such as ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, and tertiary butyl. Base, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl, 1,1,5,5-tetramethylhexyl and other straight or branched chain alkyl groups having 3 to 10 carbon atoms; cyclopropyl, cyclobutyl Cycloalkyl groups having 3 to 10 carbon atoms such as alkyl, cyclopentyl, cyclohexyl, and adamantyl are preferably n-propyl, n-butyl, and 2-ethylhexyl.

A hydrogen atom contained in a monovalent saturated hydrocarbon group having 2 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ may be substituted by a hydroxyl group, an alkoxy group or a halogen atom.

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

Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy And other alkoxy groups having 1 to 20 carbon atoms.

A monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted by a halogen atom, such as heptafluoropropyl, 1,1-difluoropropyl, 3,3,3-trifluoropropyl, nonafluorobutyl, 2 2,2-difluorobutyl, undecylpentyl, 3- (trifluoromethyl) -3,4,4,4-pentafluorobutyl, 6,6,6-trifluorohexyl, heptachloropropyl , Heptabromopropyl, 3,3,3-triiodopropyl, 2,2-dichloro-3,3,3-trifluoropropyl and the like are preferably groups represented by the following formula.

(* Indicates the junction.)

Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ include an aromatic hydrocarbon group having 6 to 10 carbons such as phenyl and naphthyl; and an aryl alkyl group having 6 to 10 carbons such as benzyl and phenethyl. And the like, and phenyl is preferred.

R ¹ , R ² , R ³ and R ⁴ aryl groups, methyl, ethyl, n-propyl alkyl groups having 1 to 20 carbon atoms; methoxy, ethoxy, propoxy, butoxy Alkoxy having 1 to 20 carbon atoms such as pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and eicosyloxy; substitution with a hydroxyl group is also possible.

The substituents of the aryl group represented by R ¹ , R ² , R ³ and R ^{4 are} preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms is more preferred.

R ¹³ is a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl , N-decyl, n-dodecyl, n-hexadecyl and n-icosyl, etc. linear alkyl groups having 1 to 20 carbon atoms; isopropyl, isobutyl, secondary butyl, tertiary butyl, Isopentyl, neopentyl, 2-ethylhexyl and other branched alkyl groups having 3 to 20 carbon atoms; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl Alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms.

Z ⁺ represents ⁺ N (R ¹³ ) ₄ , Na ⁺ or K ⁺ , and R ¹³ may 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 an alkyl group having 3 to 10 carbon atoms or a phenyl group which may have a substituent, and an alkyl group having 3 to 8 carbon atoms may be 1 to 10 carbon atoms. Alkyl substituted phenyl is preferred.

Among R ¹ , R ² , R ³ and R ⁴ , R ¹ and R ^{3 are} preferably the same group, and R ² and R ^{4 are} preferably 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 all the same, and all of them are preferably hydrogen atoms.

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

Specific examples of the dibenzopiperan dye include compounds shown below in addition to CI Acid Red 52. In the following formula, R ²⁶ and R ⁴⁰ are each independently and represent 2-ethylhexyl.

The dibenzopiperan dye (A3) may also be a commercially available dibenzopiperan dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Sinochem Chemical Co., Ltd., manufactured by Taoka Chemical Industry Co., Ltd. "Rhodamin 6G") and the compounds described below. In addition, a commercially available dibenzopiperan dye may be used as a starting material, and synthesis may be performed with reference to Japanese Patent Application Laid-Open No. 2010-32999.

The content of the dibenzopiperan 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 with respect to 100 parts by mass of the compound (a).

The dibenzopiperan dye may contain two or more kinds.

<Dibenzopiperan dye and anthocyanin dye salt>

The salt of a dibenzopiperan dye and anthocyanin dye means a salt composed of an anion derived from a dibenzopiperan compound and a cation derived from an anthocyanin compound.

The anthocyanin compound refers to a compound having a structure in the molecule that is a structure in which two heterocycles form a conjugated double bond with an odd number of methine groups.

Examples of the anion derived from a dibenzopiperan compound include the anions derived from the above-mentioned dibenzopiperan dye.

The anthocyanin compound is preferably a compound represented by the formula (1b) or a compound represented by the formula (1c).

[In formula (1b), ring Z ¹ and ring Z ² each independently represent a heterocyclic ring which may be substituted.

Y ¹ , Y ² and Y ³ each independently represent a hydrogen atom, 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 is selected from Y ¹ and Y ^{Two of 2} and Y ³ may be bonded to each other to form a ring.

u represents an integer from 0 to 3.

X ^b1- represents a counter anion, and b1 represents 1 or 2.

In formula (1c), ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ each independently represent a heterocyclic ring which may be substituted.

Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ and Y ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. The group selected from Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ and Y ⁹ may be bonded to each other to form a ring.

L ¹ represents a divalent hydrocarbon group having 1 to 16 carbon atoms which may be substituted.

v and w each independently represent an integer of 0 to 3.

X ^c1- represents a counter anion, and c1 represents 1 or 2.

The heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ contains at least one heteroatom as a constituent element of the ring, and may be a single ring or a polycyclic ring. .

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

唑環、苯并

唑環、噻唑環、苯并噻唑環、咪唑環、苯并咪唑環及喹啉環。 Examples of the heterocyclic ring include an indole ring, a benzoindole ring, a pseudoindole ring (indolenine), a benzo pseudoindole ring,

Azole ring, benzo

An azole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, and a quinoline ring.

Examples of the substituents which the heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ may have are: methyl, ethyl, propyl, isopropyl, and butyl Aliphatic hydrocarbon groups having 1 to 6 carbon atoms such as alkyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, neopentyl and tertiary pentyl; phenyl, o-tolyl, m Tolyl, p-tolyl, xylyl, mesityl, o-cumyl, m-cumyl, p-cumyl, naphthyl, and other aryl groups having 6 to 12 carbon atoms; carbons such as benzyl Aralkyls of 7 to 10; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyloxy Alkoxy groups with 1 to 6 carbon atoms; aryloxy groups with 6 to 10 carbon atoms such as phenoxy; aralkyloxy groups with 7 to 10 carbon atoms such as benzyloxy; methoxycarbonyl, ethoxycarbonyl , Propoxycarbonyl, ethenyloxy, benzamyloxy and other groups having an ester bond; methylaminesulfonyl, dimethylaminosulfonyl, ethylaminesulfonyl, diethylamine Sulfonyl, n-propylaminesulfonyl, di-n-propylaminesulfonyl, isopropylaminesulfonyl, diisopropylaminesulfonyl Alkylaminosulfonyl groups having 1 to 8 carbon atoms such as fluorenyl, n-butylaminesulfonyl, di-n-butylaminesulfonyl, 2-ethylhexylaminesulfonyl; methylsulfonyl, Carbons such as ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, secondary butylsulfonyl, tert-butylsulfonyl Alkylsulfonyl groups of 1 to 6; halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; vinyl, allyl, propylene-2-yl, methallyl, but-3-ene Alkenyl groups with 2 to 6 carbon atoms, such as -1-yl, but-3-en-2-yl, but-3-en-3-yl, and pent-4-en-1-yl; nitro; cyano, etc. .

When the substituent has a hydrogen atom, the hydrogen atom may be substituted by, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; a methoxy group, an ethoxy group, Propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary butoxy, pentyl Alkoxy groups such as oxy; aryloxy groups such as phenoxy and benzyloxy; carboxyl; cyano; nitro; allyloxy; allyloxy;

Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by Y ¹ to Y ⁹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, Amyl, isopentyl, neopentyl, hexyl, heptyl, octyl, cyclohexyl, etc.

The aryl group having 6 to 12 carbons represented by Y ¹ to Y ⁹ may be phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, mesityl, o-cumyl, m- Cumene, p-cumyl, naphthyl and the like.

The heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ is an indole ring, a benzoindole ring, a pseudo indole ring, or a benzo pseudoindole ring Preferably, an indole ring or a pseudoindole ring is preferred.

The heterocyclic ring represented by ring Z ¹ , ring Z ² , ring Z ³ , ring Z ⁴ , ring Z ⁵ and ring Z ⁶ preferably has one or two alkyl or halogen atoms 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 are preferably taken together to form a ring.

Y ¹ to Y ³ are each independently a hydrogen atom, and a cyano group or a halogen atom is preferred, and a hydrogen atom is more preferred.

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

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

u, v, and w are preferably 1 from the viewpoint of the brightness of the obtained color filter.

Examples of the divalent hydrocarbon group represented by L ¹ include alkyldiyl groups such as methylene, ethylene, ethylenediyl, propanediyl, butadiyl, tetramethylene, pentamethylene, and hexamethylene; Divalent alicyclic hydrocarbon groups such as pentadiyl, cyclohexanediyl, cyclohexenediyl, etc .; divalent aromatic hydrocarbon groups such as o-phenylene, m-phenylene, p-phenylene, and naphthyl; etc. Wait.

Examples of the substituent that the divalent hydrocarbon group may have include an amine group, a carboxyl group, a cyano group, a nitro group, a halogen atom, and a hydroxyl group.

L ^{1 may be} bonded at any position of ring Z ³ and ring Z ⁵ .

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

Or X ^b1- represented as X ^c1- counter anion, such as halide ions may be cited, ClO ₄ ^-, OH ^-, anions of organic carboxylic acids, organic sulfonic acid anion, a Lewis acid anion, an organic metal complex anion source Anions from pigments, etc.

Halide ions can be cited as Cl ^-, Br ^-, I ^- and the like.

Examples of the organic carboxylic acid anion include benzoic acid ion, alkanoate ion, trihaloalkanoate ion, nicotinic acid ion, and the like.

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

Lewis acid anion may be cited as BF ₄ ^-, SbF ₆ ^- and the like.

Examples of the anions derived from pigments include anions derived from phthalocyanin compounds and anions derived from azo compounds. Anion of phthalocyanin compound.

The organometallic complex anion is composed of a central metal and a ligand. Examples of the ligand include azo-based ligands, bisphenyldithiol-based ligands, and thioquinone chelate-based ligands. Ions, thiobisphenolate chelate system ligands, bis-diol-α-diketone system ligands, and the like. Examples of the central metal include transition metals of Groups 3 to 11 in the periodic table, such as ytterbium, yttrium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, hafnium, hafnium, iron, iron, Ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, cadmium, mercury, etc.

The above-mentioned ligands are preferably azo-based ligands and bisphenyldithiol-based ligands, and azo-based ligands are more preferred.

In terms of the above-mentioned central metal, from the viewpoints of manufacturing cost and ease of handling, cobalt, nickel, copper, and the like are preferable.

The above-mentioned organometallic complex anion, specifically, the central metal is cobalt, nickel or copper azo metal complex anion or bisphenyldithiol metal complex anion, and the central metal is cobalt, nickel Or copper azo metal complex anions are preferred.

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

[In 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 to Y ⁵ , u, X ^b1- and b1 are synonymous with the group in formula (1b).

Y ¹⁰ and Y ¹¹ each independently represent a monovalent aliphatic hydrocarbon group having 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 having 1 to 6 carbon atoms which may have a substituent, or one Y ¹² and one Y ¹³ are bonded to each other to indicate a carbon number 2 to 6 divalent aliphatic hydrocarbon groups.

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

Examples of the monovalent aliphatic hydrocarbon group include methyl, ethyl, vinyl, ethynyl, propyl, isopropyl, isopropenyl, allyl, propen-2-yl, propynyl, butyl, and isobutyl Base, secondary butyl, tertiary butyl, but-3-en-2-yl, but-1,3-dien-2-yl, pentyl, isopentyl, neopentyl, tertiary pentyl , 1-methylpentyl, 2-methylpentyl, pent-2-en-4-yl, hexyl, isohexyl, 5-methylhexyl, heptyl, octyl, etc. Aliphatic hydrocarbon group.

Examples of the substituent in the monovalent aliphatic hydrocarbon group include phenyl, o-tolyl, m-tolyl, p-tolyl, xylyl, mesityl, o-cumyl, m-cumyl, Aromatic hydrocarbon groups with 6 to 12 carbons such as cumene; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, secondary butoxy, tertiary Butoxy, pentoxy, phenoxy, benzyloxy and other alkoxy groups having 1 to 8 carbon atoms; halogen atoms such as fluorine, chlorine, bromine, and iodine; hydroxyl; carboxyl; nitro; cyanide Base and so on.

Examples of the divalent aliphatic hydrocarbon group include methylene, ethylene, propanediyl, butadiyl and the like.

Y ¹⁰ and Y ¹¹ each independently represent that an alkyl group having 1 to 8 carbon atoms which can be a halogen atom is preferable, and an alkyl group having 1 to 5 carbon atoms which can be substituted with a halogen atom is more preferable.

Y ¹² and Y ¹³ each independently represent an alkyl group having 1 to 3 carbon atoms which may be substituted by a halogen atom, and a methyl group or a trifluoromethyl group is preferred. Y ¹² and Y ^{13 are} preferably the same group.

The anthocyanin compounds include compounds represented by formula (2c-1) to compounds represented by formula (2c-19).

The cation derived from the anthocyanin compound may be a cation in the compound represented by the formula (1b) or the compound represented by the formula (2c).

Examples of the salt of the anion derived from the dibenzopiperan compound and the cation derived from the anthocyanin compound include the salts described below.

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

<Dye (A2)>

The blue or violet dye means a dye having a maximum absorption wavelength in a range of 560 nm to 650 nm when in a chloroform solution. Blue or purple dyes, preferably those with a maximum absorption wavelength in the range of 580nm to 650nm, and in the range of 600nm to 645nm Dyes with extremely large absorption wavelengths are preferred.

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

The dye (A2) may contain two or more kinds.

Triarylmethane dye (A4) is a dye containing a compound having a triarylmethane skeleton in the molecule. Examples of the triarylmethane dye (A4) include: CI Acid Violet (hereinafter, the description of CI Acid Violet is omitted, and only the numbered description is used) 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, 88, 90, 90: 1, 91, 93, 93: 1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269, CI Basic Blue 7, 81, 83, 88, 89, CI Basic Violet 2, CI Direct Blue 1, 3, 28, 29, 41, 42, 47, 52, 55, CI Food Violet 3, CI Mordant Violet 1, 1: 1, 3, 6, 8, 10, 11 , 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49, and more.

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

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

Examples of the tetraazaporphyrin dye include compounds described below.

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

Anthraquinone dye (A6) can be exemplified by: CI 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, CI Acid Violet 34, CI Acid Blue 25, 27, 40, 45, 78, 80, 112 C.I. Disperse Violet 26, 27, CI Disperse Blue 1, 14, 56, 60, C.I. Direct Blue 40, C.I. Mordant Blue 8 and so on.

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

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

[In the formula (A7), g represents an arbitrary natural number.

G ^g- represents an anion of g valence.

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 hydroxyl group, or an alkyl group, and the alkyl group contains -CH ₂ -Can also be replaced with -O-.

R ^21A and R ^22A are each independently an amino group which may be substituted. A

Examples of the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A include methyl, ethyl, n-propyl, isopropyl, n-butyl, and secondary Butyl, tertiary butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl , Cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantane-2-yl Alkyl groups having 1 to 20 carbon atoms such as 1,1- (adamantane-1-yl) alk-1-yl, "norbornyl" group, methyl "norbornyl" group and isofluorenyl group. It is preferably an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.

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

The group in which -CH ₂ -substituted with -O- contained in the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^{8A is} specifically as follows Group. Should be contained in an alkyl group having a carbon number of 1 to 10 -CH ₂ - substituted with the group -O-, an alkyl group preferably contains 1 to 6 carbon atoms, -CH ₂ - substituted with the group -O- .

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

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

The hydrogen atom contained in the amine group represented by R ^21A and R ^22A may be substituted by the following group: an aryl group which may have a substituent, an alkyl group which may have a substituent, or a propylene fluorenyl or methacryl fluorenyl group Of groups.

Among the aryl groups which may have a substituent, the aryl group may be an aryl group having 6 to 14 carbon atoms, such as phenyl, naphthyl, and anthracenyl, and the aryl group may include a halogen atom and carbon number. 1 to 8 alkyl.

Among the alkyl groups which may have a substituent, examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl, pentyl, hexyl, and heptyl , 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, Cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantane-2-yl, 1- (adamantane-1-yl) alkane-1- Alkyl groups having 1 to 20 carbon atoms, such as a methyl group, a "norylene" group, a methyl "norylene" group, and an isofluorenyl group. The -CH ₂ -group other than the -CH ₂ -group contained in the nitrogen atom may be replaced with -O-. The alkyl group may have substituents such as amine group, substituted amine group, Halogen and silicon-containing groups.

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

Examples of substituted amine groups are methylamino, ethylamino, propylamino, isopropylamine, butylamine, secondary butylamine, tertiary butylamine, dimethylamine, and diethylamine , Alkylamino groups having 1 to 8 carbons, and dialkylamino groups having 1 to 8 carbons, such as dipropylamino, ethylmethylamino, and the like.

The group containing an acrylfluorenyl group or a methacrylfluorenyl group means a group having at least one acrylfluorenyl group or a methacrylfluorenyl group as a group constituting unit.

The carbon number of the acryl- or methacryl-containing group is usually 3 to 30, preferably 3 to 20.

The group containing a propylene fluorenyl group or a methacryl fluorenyl group is preferably a group containing a propylene fluorenyl group or a methacryl fluorenyl group.

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

＊ -R ^14A -R ^15A (A7-1)

[In the formula (A7-1), R ^15A represents an acrylfluorenyl group or a methacrylfluorenyl group.

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

* Indicates a bond with a nitrogen atom. A

R ^14A is an alkanediyl group having 1 to 8 carbon atoms, such as methylene, ethylidene, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl. Base, hex-1,6-diyl, hept-1,7-diyl, oct-1,8-diyl, ethyl-1,1-diyl, propan-1,1-diyl, propan-1 , 2-diyl, propan-2,2-diyl, pent-2,4-diyl, 2-methylpropan-1,3-diyl, 2-methylpropan-1,2-diyl, Pentyl-1,4-diyl and 2-methylbut-1,4-diyl, preferably alkanediyl having 1 to 4 carbon atoms, preferably methylene or ethylene, more preferably methylene base.

Examples of the group containing an acrylfluorenyl group or a methacrylfluorenyl group are as described below. (* Indicates a bond with a nitrogen atom.)

R ^21A and R ^22A can be substituted, such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, secondary butylamine, tertiary butyl Amine, pentylamino, neopentylamino, hexylamino, dimethylamino, diethylamino, dipropylamino, diisopropylamino, ethylmethylamino, ethylisopropylamino , Ethylpropylamino, isopropylmethylamino, isopropylpropylamino, methylpropylamine, aniline, naphthylamine, 2-methylaniline, 4-methylaniline, 3-methyl Aniline, 3,5-dimethylaniline, 4-ethylaniline, N-methyl-N-aniline, acryloxymethylamino, N- (acryloxymethyl) -N -Methylamino, N- (propenyloxyethyl) -N-ethylamino, N- (methacryloxyethyl) -N-ethylamino, N- (propyleneoxyethyl ) -N-anilino, N- (acryloxyethyl) -N- (methacryloxymethyl) amino, N- (acryloxyethyloxymethyl) -N- Ethylamino and N- (methacryloxyethyloxymethyl) -N-ethylamino.

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.

唑基、異

唑基、噻唑基、異噻唑基、苯并噻唑基、苯并異噻唑基、噻吩基、苯并噻吩基等碳數2~8之雜芳香族烴基，含至少1個氮原子或硫原子以作為環構成元素的碳數2~8之雜芳香族烴基為佳。 Examples of the heteroaromatic hydrocarbon group represented by D include pyridyl, imidazolyl, pyrazolyl,

Oxazolyl, iso

Heteroaromatic hydrocarbon groups having 2 to 8 carbon atoms, such as azolyl, thiazolyl, isothiazolyl, benzothiazolyl, benzoisothiazolyl, thienyl, and benzothienyl, containing at least one nitrogen or sulfur atom A heteroaromatic hydrocarbon group having 2 to 8 carbon atoms as a ring constituent element is preferred.

The substituents that the heteroaromatic hydrocarbon group shown by D may have include an amine group that may be substituted, an alkyl group having 1 to 20 carbon atoms, and an aryl group that may have a substituent. The amine group may be substituted and may be substituted. An aryl group having a substituent.

The amine group which may be substituted may be the same as the amine group which may be substituted as shown by R ^21A and R ^22A .

The alkyl group having 1 to 20 carbon atoms may be the same as the alkyl group having 1 to 20 carbon atoms as shown in 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 phenyl, naphthyl, and anthracenyl; and the substituents include halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom, and alkyl groups having 1 to 20 carbon atoms.

The heteroaromatic hydrocarbon group represented by D is preferably a group represented by 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 amine group which may be substituted.

* Indicates a bond with a carbon atom. A

Examples of the R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A, and R ^8A alkyl groups having 1 to 20 carbon atoms as shown by R ⁵⁵ The same.

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

The optionally substituted amine group represented by R ⁵⁶ may be the same as the optionally substituted amine group represented by R ^21A and R ^22A .

R ⁵⁵ is preferably an unsubstituted or substituted aryl group, and an unsubstituted or substituted aryl group with a halogen atom is preferred.

R ^{56 is} preferably an amine group which may be substituted.

The heteroaromatic hydrocarbon group represented by D may be a group represented by formula (III-1) to a group represented by formula (III-8), and is preferably represented by formula (III-1) or formula (III-2) Group.

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

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

G ^{g- is} preferably a monovalent anion, and examples thereof include halide ions such as fluoride ion, chloride ion, bromide ion, and iodide ion; an anion represented by formula (y1); an anion represented by formula (y2); and ( y3).

[In 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 and represent a halogen atom or a halogenated hydrocarbon group, or R ^B2 and R ^B3 are combined with each other to form a ring containing -SO ₂ -N ^-- SO _2- .

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

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, secondary butyl, tertiary butyl, pentyl, hexyl, heptyl, 2- Ethylhexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl.

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

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

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

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. Specifically, it can be Fluorophenyl, chlorophenyl, bromophenyl, difluorophenyl, 1-fluoro-4-chlorophenyl, trifluorophenyl, fluoronaphthyl.

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

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

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

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

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 include fluorophenyl, chlorophenyl, bromophenyl, difluorophenyl, 1-fluoro-4-chlorophenyl, trifluorophenyl, and fluoronaphthyl.

R ^B2 and R ^{B3 are} preferably the same group.

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

The substituent which the phenyl group represented by R ^B4 and R ^B5 may have is preferably a hydroxyl group.

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

Examples of the anion represented by formula (y1) include methanesulfonic acid anion, toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion, trifluoromethanesulfonic acid anion, perfluorobutanesulfonic acid anion, phenylsulfonic acid anion, Fluorophenylsulfonic acid anions and the like.

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

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

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

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

The blue or purple dye may be a monomer or a polymer. The polymer as a blue or purple dye is a polymer containing a structural unit derived from a blue or purple dye, and may be a polymer composed of only a structural unit derived from a blue or purple dye, or a polymer containing blue Copolymers of structural units derived from color or violet dyes and other structural units (hereinafter also referred to as copolymers (a)). The structural unit derived from a blue or violet dye may be a divalent or more valent group generated by the polymerization of a polymerizable blue or violet dye, or may be formed by removing one or more hydrogen atoms from the blue or violet dye. A monovalent or higher group. As the copolymer (a), there can be mentioned, for example, a copolymer containing, in addition to the structural unit derived from a blue or purple dye, a structural unit selected from the group consisting of ethylenically unsaturated At least one of the structural units derived from the monomer of the bond and the structural unit represented by the formulas (1) to (3) described below.

The copolymer (a) may be a copolymer including a structural unit derived from a monomer introduced with a resin (B) described later and a structural unit derived from a blue or purple dye.

[In 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, may have Substituent alkylaryl or a combination thereof.

m 'represents an integer from 0 to 5. A

[In formula (2), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, and an alkylaryl group which may have a substituent Or a combination thereof.

R ¹² represents an alkyl group having 1 to 30 carbons which may have a substituent, an aryl group having 6 to 30 carbons which may have a substituent, -CO-R ¹⁷ -COOH, or a combination thereof.

R ¹⁷ represents an alkylene group having 1 to 30 carbons which may have a substituent or an alkylene group having 1 to 30 carbons which may have a substituent. A

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

R ¹⁵ represents -COOH or -CONHR ¹⁸ .

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

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

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

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

In addition, it may also include a structural unit derived from a monomer that can be copolymerized with a structural unit derived from a monomer having an ethylenically unsaturated bond, and specific examples include styrene, α-methylstyrene, and ethylene. Alkenyl aromatic monomers such as toluene and vinyl benzyl methyl ether; methacrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2- Hydroxyethyl acrylate, 2-hydroxymethyl acrylate, 2-hydroxybutyl acrylate Esters, 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate and other unsaturated carboxylic acid esters Compounds; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, unsaturated carboxylic acid such as 2-dimethylaminoethyl methacrylate Acid amino alkyl ester compounds; vinyl carboxylate compounds such as vinyl acetate and vinyl benzoate; unsaturated carboxylic acid epoxy esters such as epoxy acrylate, epoxy methacrylate, etc. Compounds; acrylic cyanide compounds such as acrylonitrile and methacrylonitrile; unsaturated amidamines such as acrylamide and methacrylamide; and combinations thereof.

The structural unit derived from the blue or purple dye contained in the copolymer (a) is selected from the structural unit derived from the triarylmethane dye (A4) and the structural unit derived from the dye represented by the formula (A7) At least one of the groups is preferred.

The structural unit derived from the triarylmethane dye (A4) is preferably a structural unit derived from the compound represented by the formula (2b-1) to the compound represented by the formula (2b-13) described above.

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.

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

Examples of the salt composed of the blue or violet dye and the compound (a) include the following.

The content of the dye (A2) is usually 80 to 10,000 parts by mass, preferably 80 to 7,000 parts by mass, preferably 80 to 1,000 parts by mass, and more preferably 80 parts by mass relative to 100 parts by mass of dibenzopiperan dye. ~ 600 parts by mass.

<Dye (Ac) and Pigment (A1)>

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

The pigment (A1) is not particularly limited, and known pigments can be used, and examples thereof include those classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

In terms of pigments, blue pigments such as C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like: purple pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc.

The colorant (A) is preferably a coloring agent containing a combination described below.

(1) Compound (a), C.I.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 purple pigment

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

The content of the colorant (A) is preferably 5 to 60% by mass relative to the total amount of the solid components, and is preferably 8 to 55% by mass, and more preferably 10 to 50% by mass.

When the content of the colorant (A) is in the foregoing range, the color density when the color filter is formed is sufficient, and the resin (B) or the polymerizable compound (C) can be formed because it has a necessary content in the composition. A pattern with sufficient mechanical strength. Here, the "total amount of solid content" in the present specification means an amount after deducting the solvent content from the total amount of the colored curable resin composition. The total amount of solid components and the content of each component relative to the total amount can be measured by a known analysis method such as liquid chromatography or gas chromatography.

<Resin (B)>

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

Resin [K1]: at least one (a) (hereinafter also referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and having a carbon number of 2 to 4 Copolymer of a cyclic ether structure and an ethylenically unsaturated bond monomer (b) (hereinafter also referred to as "(b)"); resin [K2]: (a), (b), and (a) Copolymers of copolymerized monomers (c) (but different from (a) and (b)) (hereinafter also referred to as "(c)"); resins [K3]: copolymers of (a) and (c); Resin [K4]: Resin produced by reacting the copolymer of (a) and (c) with (b); Resin [K5]: Resin produced by reacting the copolymer of (b) with (c) with (a) Resin; Resin [K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and then with a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho / meta / p-ethylene benzoic acid; maleic acid, fumaric acid, citraconic acid, mesaconic acid, and Iraq Conic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydro Unsaturated dicarboxylic acids such as phthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2 -Ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] Hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene And other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrobenzenediene Unsaturation such as formic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride Dicarboxylic acid anhydrides; mono [2- (meth) acrylic acid Unsaturated mono [(meth) acryloxyalkyl groups of polyvalent carboxylic acids, such as ethyl] succinate, mono [2- (meth) acryloxyethyl] phthalate, etc. ] Esters; such as unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule, such as α- (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) means, for example, a cyclic ether structure A polymerizable compound consisting of at least one kind of structure from the group consisting of ethylene oxide, an oxon ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloxy group.

The term "(meth) acrylic acid" as used herein means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

Examples of (b) include a monomer (a1) (hereinafter also referred to as "(b1)") having an ethylene oxide group and an ethylenically unsaturated bond, and an oxycyclobutane and an ethylenically unsaturated bond Monomer (b2) (hereinafter also referred to as "(b2)"), monomer (b3) (hereinafter also referred to as "(b3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond, and the like.

As (b1), for example, a monomer (b1-1) (hereinafter also referred to as "(b1-1)") having an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon, and having The epoxidized monomer (b1-2) of an alicyclic unsaturated hydrocarbon (hereinafter also referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth) acrylate, beta-methylglycidyl (meth) acrylate, and beta-ethylglycidyl (meth) acrylate , Epoxy propylene vinyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, p-vinyl benzyl epoxy propyl ether, α-methyl-o-vinyl benzyl epoxy propylene Ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) Base) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (epoxy Propyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, etc. .

Examples of (b1-2) include vinyl cyclohexene monoxide, 1,2-epoxy-4-ethylene cyclohexane (for example, Celloxide 2000; manufactured by Daicel), and 3,4-epoxy. Cyclohexyl meth (meth) acrylate (e.g. Cyclomer A400; manufactured by DAICEL), 3,4-epoxy cyclohexyl methyl (meth) acrylate (e.g. Cyclomer M100; manufactured by DAICEL) A compound represented by formula (I), a compound represented by formula (II), and the like.

[In formulae (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

X ^a and X ^b represents 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 junction with O. A

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

Hydroxy-substituted alkyl groups such as hydroxymethyl, 1-hydroxy Ethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1 -Hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^{b may} preferably be, for example, a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Alkyl diyl can be exemplified by methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, Hex-1,6-diyl and the like.

X ^a and X ^b may be preferably single bonds, methylene, ethylidene, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably single bonds, * -CH ₂ CH ₂ -O- (* indicates a junction with O).

Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to compounds represented by the formula (I-15). Ideally, a compound represented by the formula (I-1), a compound represented by the formula (I-3), a compound represented by the formula (I-5), a compound represented by the formula (I-7), and a formula (I-9) ) Or a compound represented by formula (I-11) to a compound represented by formula (I-15). Preferred examples include compounds represented by formula (I-1), compounds represented by formula (I-7), compounds represented by formula (I-9), or compounds represented by formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to compounds represented by the formula (II-15). Ideally, compounds represented by formula (II-1), compounds represented by formula (II-3), compounds represented by formula (II-5), compounds represented by formula (II-7), formula (II-9) ) Or a compound represented by formula (II-11) to a compound represented by formula (II-15). Preferred examples include compounds represented by formula (II-1), compounds represented by formula (II-7), compounds represented by formula (II-9) or formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used individually. Moreover, they can also be mixed in arbitrary ratios. In the case of mixing, the mixing ratio is in molar ratio. Formula (I): Formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, more preferably 20 : 80 ~ 80: 20.

As (b2), a monomer having an oxocyclobutane group and a (meth) acryloxy group is preferred. (b2) For example, 3-methyl-3-methacryloxymethyloxycyclobutane, 3-methyl-3-propenemethyloxycyclobutane, 3-ethyl 3-Methacrylmethyloxycyclobutane, 3-ethyl-3-propymethyloxycyclobutane, 3-methyl-3-methacryloxyethyl Ethoxycyclobutane, 3-methyl-3-propenyloxyethyloxycyclobutane, 3-ethyl-3-methacryloxyethyloxycyclobutane, 3-ethyl Methyl-3-propenyloxyethyloxycyclobutane and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is preferred. (b3) Specific examples include tetrahydrofuran methacrylate (for example, VISCOAT V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, and the like.

From the reliability of heat resistance and chemical resistance of the obtained color filter From a more elevated viewpoint, (b1) is preferred as (b). Furthermore, (b1-2) is preferable because the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, secondary butyl (meth) acrylate, and tertiary (meth) acrylate Butyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate , Cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the technical field As a common name in China, it is also called "dicyclopentyl (meth) acrylate"; it is also called "tricyclodecyl (meth) acrylate"), and tricyclic [5.2.1.0 ^2,6 ] decane Alkenyl-8-yl (meth) acrylate (also commonly referred to in the art as "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (methyl ) Acrylate, isoamyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) Acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylic (Meth) acrylates, etc .; hydroxyl-containing (meth) acrylates, such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate; diethyl maleate , Dicarboxylic acid diesters such as diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethyl Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 ' -Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene , 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'- (Hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl 5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1 ] Hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tertiary butoxy Group) Bicyclic unsaturated compounds such as bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene; N-phenyl male Fluorenimine, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide Methyl-4-maleimide iminobutyrate, N-succinimide imino-6-maleimide hexanoate, N-succinimide imino-3-maleimide propionate , N- (9-acridinyl) maleimide and other dicarbonylamide derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, P-methoxystyrene, acrylonitrile, methacrylonitrile, ethylene chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide Amidine, bicyclo [2.2.1] hept-2-ene, etc. are suitable.

In the resin [K1], the ratio of the structural units derived from the respective substances to the total structural units constituting the resin [K1] is preferably as follows: Tectonic units derived from (a); 2 ~ 60 mole%, tectonic units derived from (b); 40 ~ 98 mole%, preferably with the following: tectonic units derived from (a); 10 ~ 50 Mol%, the structural unit derived from (b); 50 ~ 90 Mol%.

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, the developability when a colored pattern is formed, and the solvent resistance of the obtained color filter tend to be excellent.

For the resin [K1], refer to, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing House Co., Ltd., 1st edition, 1st issue, March 1, 1972) and the document Citations to make.

Specifically, the following methods can be mentioned: a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and heating is performed while stirring in a deoxidizing environment by replacing oxygen with nitrogen, for example; Insulation. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those commonly used in this field can be used. For example, the polymerization initiator may be, for example, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide Materials (such as benzamyl peroxide) and the like, and the solvent may be any substance that dissolves each monomer, and the solvent (E) as the coloring curable resin composition of the present invention is mentioned below.

In addition, the obtained copolymer may be a solution after the reaction, a concentrated or diluted solution, or a solid (powder) which is taken out by a method such as reprecipitation. In particular, by using the color sensitive of the present invention The solvent contained in the photosensitive resin composition can be used as a solvent during the polymerization, and the solution after the reaction can be used for the preparation of the colored photosensitive resin composition of the present invention. Therefore, the coloring photosensitive resin composition of the present invention can be simplified. Process.

In the resin [K2], the ratio of the structural units derived from the respective substances is based on the total structural units constituting the resin [K2], which is preferably the following: the structural unit derived from (a); 2 to 45 mole%, Tectonic units derived from (b); 2 ~ 95 mole%, tectonic units derived from (c); 1 ~ 65 mole%, and preferably the following: tectonic units derived from (a); 5 ~ 40 Morse% originates from the structural unit of (b); 5 ~ 80 Morse% originates from the structural unit of (c); 5 ~ 60 Morse%.

Once the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the solvent resistance, heat resistance, and mechanical strength of the obtained color filter are increased. Tends to be excellent.

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

Among the resins [K3], the ratio of the structural units derived from the respective substances to the total structural units constituting the resin [K3] is preferably the following: the structural units derived from (a); 2 to 60 mole%, Derived from the structural unit of (c); 40 ~ 98 mole%, and the following are preferred: Tectonic units derived from (a); 10 ~ 50 mole%, tectonic units derived from (c); 50 ~ 90 mole%.

The resin [K3] can be produced by, for example, the same method as that described as the production method of the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and (b) a cyclic ether having 2 to 4 carbon atoms, a carboxylic acid having (a), and / Or the carboxylic anhydride is subjected to an addition reaction.

First, the copolymer of (a) and (c) is produced by the same method as described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from the respective substances should be the same as those listed in the resin [K3].

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

Continuing the production of copolymers of (a) and (c), replacing the ambient gas in the flask from nitrogen with air, and reacting (b), the reaction catalyst of carboxylic acid or carboxylic anhydride with cyclic ether (such as tris (dimethyl) Aminomethyl) phenol, etc.) and polymerization inhibitors (for example, hydroquinone, etc.) are put into the flask, and the resin [K4] can be produced by, for example, reacting at 60 to 130 ° C for 1 to 10 hours.

The amount of (b) is preferably 5 to 80 mol, and more preferably 10 to 75 mol relative to 100 mol of (a). By setting it as this range, the balance of the storage stability of a coloring curable resin composition, the developability at the time of pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern will become favorable. The cyclic ether is highly reactive and unreacted (b) is unlikely to remain. Therefore, (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).

The amount of the aforementioned reaction catalyst 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 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 reaction conditions such as the feeding method, reaction temperature, and time can be appropriately adjusted by taking into consideration the heat generation caused by manufacturing equipment or polymerization. In addition, the polymerization conditions are the same, and the amount of heat generated by the manufacturing equipment or polymerization can be considered, and the feeding method or reaction temperature can be appropriately adjusted.

Resin [K5], as the first stage, a copolymer of (b) and (c) can be obtained in the same manner as the method for producing the above-mentioned resin [K1]. In the same manner as above, the obtained copolymer may be used as a solution after the reaction, a concentrated or diluted solution may be used, or a solid (powder) removed by a method such as reprecipitation may be used.

The ratio of the structural units derived from (b) and (c), relative to the total moles of the total structural units constituting the aforementioned copolymer, should be: the structural units derived from (b); 5 ~ 95 mole%, 5 ~ 95 mole% from tectonic units derived from (c), preferably: tectonic units from (b); 10 ~ 90 mole% from tectonic units from (c); 10 ~ 90 moles ear%.

Furthermore, according to the same conditions as the method for producing the resin [K4], the carboxylic acid or carboxylic acid anhydride contained in (a) and the copolymer derived from (b) and (c) derived from (b) The cyclic ether is reacted to obtain a resin [K5].

The amount of (a) used to react the copolymer is relative to 100 Moore (b) is preferably 5 to 80 Moore. Since the cyclic ether is highly reactive and unreacted (b) remains, the (b) used for the resin [K5] is preferably (b1), and more preferably (b1-1).

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

A carboxylic acid anhydride is made to react with the hydroxyl group produced by reaction of a cyclic ether and a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1, 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (Himic anhydride) and the like. The amount of carboxylic anhydride is preferably 0.5 to 1 mole relative to 1 mole of (a).

As for the resin (B), specific examples include resin [K1], such as 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic copolymer, 3,4-epoxy Tricyclic [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic copolymer, etc .; resin [K2], such as epoxypropyl (meth) acrylate / benzyl (meth) acrylate / ( (Meth) acrylic acid copolymer, epoxypropyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate / ( (Meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloxymethyloxyfluorene / (meth) acrylic acid / styrene copolymer, etc .; resin [K3], such as benzyl (meth) acrylate / (meth) acrylic copolymer, styrene / (meth) acrylic copolymer, etc .; resin [K4], such as glycidyl (meth) acrylate Resin formed by addition reaction of benzyl (meth) acrylate / (meth) acrylic acid copolymer, and tricyclodecyl (meth) acrylate / styrene made of glycidyl (meth) acrylate / (Meth) acrylic copolymer Resin and the like obtained by the addition reaction of glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; resin [ K5], such as a resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer, and Resin produced by the reaction of decyl (meth) acrylate / styrene / epoxypropyl (meth) acrylate copolymer; resin [K6], such as tricyclodecyl (meth) acrylic acid A resin obtained by reacting a (meth) acrylate / epoxypropyl (meth) acrylate copolymer and a resin further reacted with tetrahydrophthalic anhydride, and the like.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, preferably 5,000 to 50,000, and more preferably 5,000 to 30,000. If the molecular weight is within the above range, the coating film hardness will increase, the residual film rate will also be high, the solubility to the developer in the unexposed portion will be good, and the resolution of the colored pattern will tend to increase.

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, preferably 60 to 150, and more preferably 70 to 135 mg-KOH / g. The acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be used, for example, by using The potassium hydroxide aqueous solution was determined by titration.

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

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and the like. A (meth) acrylate compound is preferred.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetraneopenta Tetraol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, tris (2- (meth) acryloxyethyl) trimer isocyanate, ethylene glycol modified neopentyl Alcohol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol Hexa (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc.

Among them, dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate are preferred.

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 7 to 65% by mass, preferably 13 to 60% by mass, and more preferably 17 to 55% by mass with respect to the total solid content. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film rate and the color filter chemical resistance when the colored pattern is formed are improved.

<Polymerization initiator (D)>

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

化合物、醯基膦氧化物化合物、O-醯基肟化合物及聯咪唑化合物所構成之群組中至少1種的聚合起始劑為佳，而含O-醯基肟化合物的聚合起始劑較佳。 The polymerization initiator (D) is selected from the group consisting of

At least one of the polymerization initiators in the group consisting of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound is preferable. good.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzyloxy-1 -(4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane -1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethane- 1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolylmethyl) Oxy) benzyl} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxy-1--1- (9-ethyl-6- (2-methylbenzene (Methylamino) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2-methyl Benzamidine) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as IRGACURE OXE01, OXE02 (above, manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Of which O-fluorenyl oxime compounds Preferably, it is selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, N-benzyloxy-1- ( 4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1 At least one of the group consisting of -keto-2-imine, and more preferably N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2- Imine. If it is such an O-fluorenyl oxime compound, a high-brightness color filter tends to be obtained.

啉基-1-(4-甲基硫基苯基)丙-1-酮、2-二甲基胺基-1-(4-

啉基苯基)-2-苄基丁-1-酮、2-(二甲基胺基)-2-[(4-甲基苯基)甲基〕-1-[4-(4-

啉基)苯基]丁-1-酮、2-羥基-2-甲基-1-苯基丙-1-酮、2-羥基-2-甲基-1-[4-(2-羥基乙氧基)苯基]丙-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙-1-酮的寡聚物、α,α-二乙氧基苯乙酮、苄基二甲基縮酮等。亦可使用IRGACURE 369，907，379(以上，BASF公司製)等市售品。 Examples of the aforementioned alkylphenyl ketone compound are 2-methyl-2-

Phenyl-1- (4-methylthiophenyl) propan-1-one, 2-dimethylamino-1- (4-

Phenylphenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-

Phenyl) phenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethyl (Oxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer , Α, α-diethoxyacetophenone, benzyldimethylketal and the like. Commercial products such as IRGACURE 369, 907, 379 (above, manufactured by BASF) can also be used.

化合物可舉如2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(4-二乙基胺基-2-甲基苯基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三

等。 three

Compounds such as 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris

, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri

, 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri

, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris

, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris

, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris

, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris

, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris

Wait.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercial products such as IRGACURE (registered trademark) 819 (manufactured by BASF) can also be used.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorobenzene) Base) -4,4 ', 5,5'-tetraphenylbiimidazole (refer to, for example, Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis ( 2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkane) Oxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (refer to, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204 Etc.), imidazole compounds in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Laid-Open No. 7-10913).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. ; Benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3 ', 4, 4'-tetrakis (third butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethyl Anthraquinone, camphorquinone, and other quinone compounds; 10-butyl-2-chloroacridone, benzyl or phenylglyoxylate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiator (D1) (especially amines) described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethoxyloxyphenyldimethylsulfonium p-toluene. Sulfonate, 4-Ethyloxyphenylmethylbenzyl hexafluoroantimonate, triphenyl sulfonium p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyliodonium p-toluene Sulfonates, onium salts such as diphenyliodonium hexafluoroantimonate, nitrobenzyl toluene sulfonates, benzoin toluene sulfonates, and the like.

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

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

化合物及羧酸化合物等。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxysulfur.

Compounds and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethyl Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4 '-Bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( B Of these, 4,4'-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

化合物可舉如2-異丙基9-氧硫

、4-異丙基9-氧硫

、2,4-二乙基9-氧硫

、2,4-二氯9-氧硫

、1-氯-4-丙氧基9-氧硫

等。 9-oxysulfur

Compounds such as 2-isopropyl 9-oxysulfur

, 4-isopropyl 9-oxysulfur

, 2,4-diethyl 9-oxysulfur

, 2,4-dichloro 9-oxysulfur

, 1-chloro-4-propoxy9-oxysulfur

Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxy Phenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N -Naphthyl glycine, naphthoxyacetic acid, and the like.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 100 parts by mass relative to the total amount of the resin (B) and the polymerizable compound (C). ~ 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed at a high sensitivity and the color filter productivity tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples include an ester solvent (a solvent containing -COO- and no -O- in the molecule), an ether solvent (a solvent containing -O- and -COO- free in the molecule), Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- and -COO-free in the molecule), alcohol solvent (containing OH in the molecule and free of -O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene and the like.

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

烷、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚、苯甲醚、苯乙醚及甲基苯甲醚等。 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, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3 -Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropiperan, 1,4-di

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, benzyl Ether, phenyl ether and methyl anisole.

Examples of the ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy 2-methylpropionic acid Ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono Propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether ethyl Acid esters, dipropylene glycol methyl ether acetate, and the like.

Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone, isophorone and so on.

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

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

Examples of the amidine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoints of coating properties and drying properties, organic solvents having a boiling point of 120 ° C. or higher and 180 ° C. or lower at 1 atm are preferred. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether Ethyl lactate and ethyl 3-ethoxypropionate are preferred.

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

<Leveling agent (F)>

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

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, for example, Toray Silicone DC3PA, the same as SH7PA, the same as DC11PA, the same as SH21PA, the same as SH28PA, the same as SH29PA, the same as SH30PA, and the same as SH8400 (trade names: Toray Dow-Corning (stock) system), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan LLC), etc.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430, same FC431 (Sumitomo 3M (share) system), MEGAFAC (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same F554, same R30, the same as RS-718-K (DIC (share) system), EFTOP (registered trademark) EF301, the same EF303, the same EF351, the same EF352 (Mitsubishi Materials Electronics Corporation (share) system), SURFLON (registered trademark) S381, the same S382, same as SC101, same as SC105 (made by Asahi Glass) and E5844 (made by Daikin Fine Chemical) Research Institute) and so on.

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, same BL20, same F475, same F477, and F443 (DIC (shares) system).

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1% by mass or less, and preferably 0.01% by mass or more with respect to the total amount of the coloring curable resin composition. 0.05 mass% or less. When the content of the leveling agent (F) is within the aforementioned range, the flatness of the color filter can be made good.

<Other ingredients>

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

<Manufacturing method of colored curable resin composition>

The colored curable resin composition of the present invention can be prepared by, for example, mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E), if necessary, used for adjustment. A leveling agent (F), a polymerization initiator (D1), and other ingredients are prepared.

The dye (A2) and the dye (Ac) used as needed should be dissolved in part or all of the solvent (E) in advance to prepare a solution. The solution should be filtered through a filter with a pore size of about 0.01 to 1 μm .

The blue pigment (A1) should be mixed with some or all of the solvent (E) in advance and dispersed with a bead mill or the like until the average particle diameter of the pigment reaches About 0.2 μm or less. In this case, part or all of the pigment dispersant and resin (B) may be mixed as necessary. The target coloring curable resin composition can be prepared by mixing the remaining components in the obtained pigment dispersion liquid to a predetermined concentration.

The mixed colored hardening resin composition is preferably filtered through a filter having a pore size of about 0.01 to 10 μm .

According to the colored curable resin composition of the present invention, a color filter having excellent heat resistance can be produced. This color filter is suitable for use as a color filter for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Examples

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

In the examples, "%" and "part" are mass% and mass parts unless otherwise specified.

In the following synthesis examples, compounds were identified using a mass analyzer (LC; Model 1200 manufactured by Agilent, MASS; LC / MSD model manufactured by Agilent) or an elemental analyzer (VARIO-EL; (manufactured by Elemertar Corporation)).

[Synthesis Example 1]

In a reactor, 32.3 parts of pararosaniline hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 500 parts of absolute ethanol, refluxed for 8 hours, and cooled to room temperature. 20.2 parts of the compound represented by formula (a2-1) was slowly dropped into the obtained mixture over 5 hours. After the dropwise addition, the resulting mixture was stirred at 70 ° C. for 36 hours. After cooling to room temperature, 48.8 parts of a compound represented by formula (a2) was obtained.

[Synthesis Example 2]

To 28.52 parts of bisN-ethyl-N-hydroxyethylaminodiphenyl ketone and 17.80 parts of triethylamine, 50 mL of dichloromethane was added and dissolved by stirring. Thereafter, 13.56 parts of methacrylic anhydride was added, and the temperature was raised to 40 ° C and the temperature was maintained. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, the layers were separated, and 20 mL of saturated saline was added and stirred for 30 minutes. After the layers were separated, the organic layer was distilled off, and the residual solid was dried under reduced pressure to obtain 21.4 parts of a compound represented by the formula (aa2).

21.4 parts of a compound represented by formula (aa2) was added to 500 mL of chloroform and stirred. Thereafter, 49.08 parts of phosphorus oxychloride was added and stirred for 15 minutes. After adding 14.56 parts of N-phenyl-1-naphthylamine, it refluxed. After completion of the reaction, the reaction solution was cooled to room temperature, and water was added thereto, followed by stirring. After stirring, it was allowed to stand to separate the layers, and the organic layer was distilled off. The residual solid was dried under reduced pressure and purified to obtain formula (aa3). 20.3 parts of the compound shown.

[Synthesis Example 3]

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

[Synthesis Example 4-7]

In a flask equipped with a cooling tube and a stirrer, the monomers represented by formula (aa5), benzyl methacrylate, methacrylic acid, methyl methacrylate, and N-benzyl ma were added in a weight ratio as shown in Table 1 below. With respect to 100% by weight of the total amount of the foregoing monomers, 6% by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) (starter) is added to lyme imine. Next, 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, and the mixture was then placed in a nitrogen ring. Start stirring slowly in the environment. The reaction solution was heated to 90 ° C. and stirred for 10 hours to obtain a copolymer solution.

[Synthesis Example 8]

The following reactions were performed under a nitrogen atmosphere. After placing 36.3 parts of potassium thiocyanate and 160.0 parts of acetone in a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. Next, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped over 10 minutes. After the dropping was completed, the mixture was stirred at room temperature for another 2 hours. Next, after ice-cooling the reaction mixture, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the dropping was completed, the mixture was stirred at room temperature for another 30 minutes. Next, after cooling the reaction mixture under ice, 34.2 parts of a 30% sodium hydroxide aqueous solution was added dropwise. After the dropping was completed, the mixture was stirred at room temperature for another 30 minutes.

Next, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After the dropping was completed, the mixture was stirred under reflux for 7 hours. Next, after the reaction mixture was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, and then 200 parts of toluene was added and stirred for 30 minutes. Then the stirring was stopped for 30 minutes, and then the organic layer and the aqueous layer were separated. After the water layer was drained by the liquid separation operation, the organic layer was washed with 200 parts of an equivalent concentration of hydrochloric acid, then washed with 200 parts of tap water, and finally washed with saturated water. Wash with 200 parts of salt water. An appropriate amount of thenardite (sodium sulfate hydrate) was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 52.0 parts of a compound represented by the formula (B-I-1). Yield 50%

[Synthesis Example 9]

The following reactions were performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 9.3 parts of a compound represented by formula (BI-1) and 4,4'-bis (diethylamino) diphenyl ketone (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged. ) After 10.0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added, and the mixture was stirred at 95 to 100 ° C for 3 hours. Next, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated saline, and then 100 parts of toluene was added and stirred for 30 minutes. Then the stirring was stopped and left for 30 minutes, and then separated into an organic layer and an aqueous layer. After the water layer was drained by a liquid separation operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of thenardite (sodium sulfate hydrate) was added to the organic layer and stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent was distilled off from the obtained organic layer by an evaporator to obtain a blue-violet solid. The blue-violet solid was dried under reduced pressure at 60 ° C. 19.8 parts of a compound represented by the formula (A-I-a1) was obtained. 100% yield

Identification of compounds represented by formula (A-I-a1)

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

Exact Mass: 636.3

[Synthesis Example 10]

The following reactions were performed under a nitrogen atmosphere. In a flask equipped with a cooling tube and a stirring device, 10.0 parts of a compound represented by the formula (AI-a1), 4.5 parts of lithium bis (trifluoromethanesulfonate) imide (manufactured by Tokyo Chemical Industry Co., Ltd.) and N After 100.0 parts of N-dimethylformamide, it was stirred at 50 to 60 ° C for 3 hours. Next, after the reaction mixture was cooled to room temperature, 2000.0 parts of tap water was dripped while stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was turbid to obtain a blue-green solid. The blue-green solid was dried under reduced pressure at 60 ° C to obtain 11.3 parts of a compound represented by the formula (A-I-a9). The yield was 82%.

[Synthesis Example 11]

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was introduced at 0.02 L / min to create a nitrogen atmosphere. 305 parts by mass of ethyl lactate was placed therein, and heated to 70 ° C. while stirring.

Next, 46 parts by mass of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (I-1) and a formula (II- 1) Compound shown in 240) was dissolved in 185 parts by mass of ethyl lactate to prepare a solution, and the solution was dropped into a flask kept at 70 ° C. using a dropping funnel over 4 hours.

On the other hand, a solution obtained by dissolving 30 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was used in another dropping funnel. It was dripped into the flask over 4 hours. After the dripping of the polymerization initiator solution was completed, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight Mw of 9.1 × 10 ³ , a molecular weight distribution of 2.1, a solid content of 26% by mass, and a solid content acid value 120 mg-KOH / g of resin B1 solution. The resin B1 has the following structural units.

[Synthesis Example 12]

In a flask equipped with a stirrer, a thermometer, a reflux cooling tube, a dropping funnel, and a nitrogen introduction tube, 182 parts of propylene glycol monomethyl ether acetate was charged. After the ambient gas in the flask changed from air to nitrogen, the temperature was increased to 100 ° C. Add the following solution dropwise and continue stirring at 100 ° C: 70.5 parts of benzyl methacrylate, 43.0 parts of methacrylic acid, and tricyclodecane skeleton monomethacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) 22.0 To a mixture of 136 parts of propylene glycol monomethyl ether acetate and 3.6 parts of 2,2'-azobisisobutyronitrile was added.

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

The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.

Installation; K2479 ((share) Shimadzu Corporation)

Column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL / min

Detector; RI

Calibration reference materials; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by TOSOH)

The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight to the number average molecular weight was defined as the "molecular weight distribution".

[Synthesis Example 13]

Instead of the N-phenyl-1-naphthylamine in Synthesis Example 2, a compound represented by Formula (BI-1) was used, and a compound represented by Formula (aa13) was obtained in the same manner as in Synthesis Example 6. .

[Synthesis Examples 14-17]

A copolymer solution was obtained in the same manner as in the aforementioned Synthesis Examples 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-toluene-1,3-disulfonic acid, 15.6 parts of N, N-dibutyl-3-aminophenol, and 2.2 parts of sodium p-toluenesulfonate were stirred at 120 degrees for 12 hours. After cooling, the obtained mixture was added to 100 parts of a 50% aqueous solution of ethanol and filtered to obtain a compound represented by the formula (I-2).

[Synthesis Example 19]

After 10.00 parts of the compound represented by formula (aa3) was dissolved in 100 mL of methanol, 2.50 parts of sodium trifluoromethanesulfonate was added as a substituted salt. After filtration, the obtained compound was washed with water, and the residual solid was dried under reduced pressure to obtain 5.5 parts of a compound represented by the formula (aa4).

[Synthesis Example 20]

After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by the formula (aa4) and 0.16 parts of 2,2'-azobisisobutyronitrile were dissolved in 20 parts of methyl ethyl ketone, and the reaction mixture was kept at 70 ° C for 3 hours. After the completion of the addition, it was maintained at 70 ° C for 8 hours. After concentrating the methyl ethyl ketone, hexane was added to the reaction solution to precipitate crystals, followed by filtration, washing of residual solids with hexane, and drying under reduced pressure to obtain a polymer. Compound (aa4) 1.80 parts.

[Synthesis Example 21]

After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by formula (aa4) and 0.25 parts of 2,2'-azobisisobutyronitrile, 0.51 parts of benzyl methacrylate, 0.51 parts of methacrylic acid, and 0.42 parts of N-phenylmaleimide It was dissolved in 50 parts of methyl ethyl ketone and kept at 70 ° C in the reactor for 3 hours. After the completion of the addition, it was maintained at 70 ° C for 8 hours. After concentrating the methyl ethyl ketone, hexane was added to the reaction solution to precipitate crystals, and then filtered. The remaining solid was washed with hexane and dried under reduced pressure to obtain polymerization. Compound (aa4 ') 2.35 parts.

[Synthesis Example 22]

After adding 30 parts of methyl ethyl ketone under a nitrogen atmosphere, the temperature was raised to 70 ° C. 2.54 parts of the compound represented by formula (aa5) and 0.16 parts of 2,2'-azobisisobutyronitrile were dissolved in 20 parts of methyl ethyl ketone, and the mixture was charged at 70 ° C for 3 hours. After the completion of the addition, it was maintained at 70 ° C for 8 hours. After concentrating the methyl ethyl ketone, hexane was added to the reaction solution to precipitate crystals, and then filtered. The residual solid was washed with hexane and dried under reduced pressure to obtain polymerization. Compound (aa5) 1.63 parts.

[Synthesis Example 23]

30 parts of methyl ethyl ketone was put under a nitrogen atmosphere, and the temperature was raised to 70 ° C. 2.54 parts of the compound represented by formula (aa5) and 0.25 parts of 2,2'-azobisisobutyronitrile, 0.51 parts of benzyl methacrylate, 0.51 parts of methacrylic acid, and 0.42 parts of N-phenylmaleimide In 50 parts of methyl ethyl ketone, the reactor was maintained at 70 ° C. for 3 hours. After the completion of the addition, the solution was maintained at 70 ° C for 15 hours. After concentrating the methyl ethyl ketone, hexane was added to the reaction solution to precipitate crystals, followed by filtration, and the residual solid was dried under reduced pressure to obtain a polymer compound (aa5 '). 3.80 servings.

[Synthesis Example 24]

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

[Synthesis Example 25]

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

[Synthesis Examples 26-29]

In a flask equipped with a cooling tube and a stirrer, the monomers represented by formula (aa8), benzyl methacrylate, methacrylic acid, methyl methacrylate, and N-benzyl were added at the weights shown in Table 3 below, respectively. For maleimide, 6 parts by weight of 2,2′-azobisisobutyronitrile and benzyl methacrylate were added as starting agents to 100 parts by weight of the total amount of the aforementioned monomers. Next, 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added as a solvent with respect 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 was heated to 90 ° C. and stirred for 10 hours to obtain a copolymer solution.

[Synthesis Examples 30-33]

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

[Synthesis Examples 34-37]

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

[Synthesis Example 38]

After 2.1 parts of Basic Blue 7 (Tokyo Kasei Co., Ltd.) was dissolved in 100 parts of methanol, 2.1 parts of a compound represented by the following formula (Pc) (manufactured by Aldrich) was added, and the mixture was stirred at room temperature for 12 hours. 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 degrees for 24 hours to obtain a compound represented by the formula (a-4).

[Example 1] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

(A) Colorant: 1.0 part of C.I. Acid Red 52

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 2] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF company Secretary) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 3] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

(A) Colorant: 0.5 parts of C.I. Acid Red 52

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 4] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

(A) Colorant: 5.8 parts of a compound represented by formula (a2)

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 5] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

(A) Colorant: 0.5 parts of C.I. Acid Red 52

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 6] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

(A) Colorant: 0.5 parts of C.I. Acid Red 52

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 7] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 8] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 9] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 10] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 11] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 12] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 13] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 14] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 15] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 16] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Example 17] (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 (aa4) obtained in Synthesis Example 7 was used instead of the dibenzopiperan dye.

[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 formula (aa5) obtained in Synthesis Example 8 was used instead of the dibenzopiperan 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 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 the 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 formula (a2).

[Example 22] (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 (aa6) obtained in Synthesis Example 24 was used instead of the compound represented by the 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 liquid obtained in Synthesis Example 26 was used instead 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 liquid 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 liquid obtained in Synthesis Example 28 was used instead 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 liquid obtained in Synthesis Example 29 was used instead 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 liquid obtained in Synthesis Example 30 was used instead 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 liquid obtained in Synthesis Example 31 was used instead 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 liquid obtained in Synthesis Example 32 was used instead 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 liquid obtained in Synthesis Example 33 was used instead 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 liquid obtained in Synthesis Example 34 was used instead 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 liquid obtained in Synthesis Example 35 was used instead 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 liquid obtained in Synthesis Example 36 was used instead 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 liquid obtained in Synthesis Example 37 was used instead of the compound represented by the formula (a2).

[Example 38] (Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the compound represented by the formula (a2) was used, and the compound represented by the formula (a2) was further contained C.I. Pigment Violet 23.

[Example 39] (Preparation of colored curable resin composition)

A colored curable resin composition was obtained in the same manner as in Example 3, except that the compound represented by the formula (1-44) was used instead of the compound represented by the formula (a2) and further containing C.I. Pigment Violet 23.

[Comparative Example 1] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

(C) Polymerizable compound: Dinepentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; made by Nippon Kayaku Co., Ltd.) 50 copies

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 600 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

[Comparative Example 2] (Preparation of colored curable resin composition)

The following are mixed to obtain a colored curable resin composition:

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

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

(C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D) Polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) oct-1-one-2-imine (IRGACURE (registered trademark) OXE 01; BASF Corporation System) 10 servings

(F) Leveling agent: Polyether modified silicone oil (Toray Silicone SH8400: manufactured by Toray-Dow Corning)

(E) Solvent: 550 parts of ethyl lactate

(E) Solvent: 10 parts of propylene glycol monomethyl ether acetate.

<Creation of colored patterns>

A colored curable resin composition was applied to a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Corporation) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to obtain a colored layer.

After leaving to cool, the substrate with the colored layer formed was separated from the quartz glass photomask by 100 μm , and exposed using an exposure machine (TME-150RSK; manufactured by Topcon) at an ambient temperature of 150 mJ / cm ² Amount (reference at 365nm) of light. A mask formed with a 100 μm line and space pattern was used. The colored layer after light irradiation is immersed in an aqueous developing solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C for 60 seconds. After washing with water, post-baking at 200 ° C for 30 minutes in an oven. Get a colored pattern.

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured using the film-thickness measuring device (DEKTAK3; Japan Vacuum Technology Co., Ltd.).

<Chroma Evaluation>

With respect to the obtained colored pattern, a spectrometer (OSP-SP-200; manufactured by Olympus Co., Ltd.) was used to measure the spectrometry, and a characteristic coefficient of the C light source was used to measure the xy chromaticity coordinates (x, y) and three in the XYZ color system of CIE. Stimulus value Y. A larger Y value indicates higher brightness.

[Evaluation of heat resistance]

The coating film of the obtained colored photosensitive resin composition was heated at 230 ° C for 20 minutes, and the color difference (ΔEab *) before and after the coating film was heated was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). As a result of applying the above-mentioned heat resistance evaluation to the obtained coating film, the color difference (ΔEab *) is shown in Tables 6 to 9. The smaller ΔEab * indicates that the color change before and after heating is more excellent in heat resistance.

[TABLE 6]

Industrial availability

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

Claims (2)

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) includes a compound represented by formula (a), And at least one selected from the group consisting of dibenzopiperan dyes, and salts of dibenzopiperan dyes and anthocyanin dyes, wherein the dibenzopiperan dye is CI acid 52 or Compound represented by the following formula (I) Wherein, k1, k2, k3 and k4 based independently of each represent an integer of 0 to 4, and 1 ≦ k1 + k2 + k3 + k4 ≦ 16; X a -, X b -, X c - and X _d ^- based and each independently represent -CO ₃ ^- or ^{_{-SO 3 -; A a +,}} A b +, A c + A _d ⁺ line and each independently represents a cation and a sodium ion, a potassium ion, or of formula (b), of: In formula (b), R ¹⁰⁰ , R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are each independently and 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 independently of each system represent a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ^+; Z ⁺ each independently represent 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, and R ¹³ may be the same or different; X ⁺ each independently represents Na ⁺ or K ⁺ ; a represents an integer of 1 to 4; The colored curable resin composition according to claim 1, wherein the colorant (A) further comprises a blue or purple dye (A2).