KR20160051625A - Colored curable resin composition - Google Patents

Abstract

Provided is a color filter having excellent heat resistance and excellent brightness. A colored curable resin composition comprises a blue pigment (A1), a compound represented by formula (I), resin (B), a polymerizable compound (C) and a polymerization initiator (D). (In formula (I), R1, R2, R3 and R4 are independently a monovalent saturated hydrocarbon group having carbon number of 3 to 10 allowed to have a substituent, or an aryl group allowed to have a substituent. R51, R52, and R53 are independently a hydrogen atom, SO_3-, -SO_3H, -SO_3-Z^+. X^+ and Z^+ are independently +N(R13)_4, Na^+, or K^+, R13 is a hydrogen atom or a monovalent saturated hydrocarbon group having carbon number of 1 to 20. Four R13s in +N(R13)_4 can be same or different. a is an integer number of one to four.)

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

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

Patent Document 1 discloses a colored curable resin composition comprising CI Pigment Blue 15: 6 and CI Acid Red 52 as a colorant and a dye represented by the following formula: CI Pigment Blue 15: 6 And 14.7 parts by mass based on 100 parts by mass of the coloring curable resin composition.

Japanese Unexamined Patent Application Publication No. 2013-144724

The colored curable resin composition of the present invention is intended to obtain a color filter excellent in heat resistance and brightness.

The present invention includes the following inventions.

[1] A colored curable resin composition comprising a blue pigment (A1), a compound represented by the following formula (I), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

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

R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.

X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.

and a represents an integer of 1 to 4.]

[2] The colored curable resin composition according to [1], further comprising a blue or violet dye (A2).

[3] The colored curable resin composition according to [1], wherein the blue pigment (A1) is CI Pigment Blue 15: 6.

[4] The blue or purple dye (A2)

The xanthene dyes (A3) other than the compound represented by the formula (I)

Triarylmethane dyes (A4),

Formula (A7):

[In the formula (A7)

g represents an arbitrary natural number.

G ^g- represents anion of g.

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

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

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

And a dye represented by the general formula

A polymer comprising a structural unit derived from the dye represented by the above formula (A7)

[2] The colored curable resin composition according to [2], wherein at least one selected from the group consisting of

[5] The blue or violet dye (A2)

Triarylmethane dyes (A4),

A dye represented by the formula (A7)

A polymer comprising a structural unit derived from the dye represented by the above formula (A7)

[4] The colored curable resin composition according to [4], wherein the coloring curable resin composition is at least one selected from the group consisting of

[6] A colorant comprising a triarylmethane dye (A4), a blue pigment (A1) and a compound represented by the formula (I), wherein the triarylmethane dye (A4) is a polymer.

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

R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.

X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.

and a represents an integer of 1 to 4.]

[7] Formula (A7)

[In the formula (A7)

g represents an arbitrary natural number.

G ^g- represents anion of g.

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

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

R ^21A and R ^22A each independently represent an optionally substituted amino group, and a polymer containing a constituent unit derived from the dye represented by the formula (A7) A dye of the species,

A blue pigment A1,

Formula (I):

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

R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.

X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.

and a represents an integer of 1 to 4. 2. The colorant according to claim 1,

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

[9] A color filter formed from the colored curable resin composition according to any one of [1] to [5].

[10] A display device including the color filter according to [9].

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

The colored curable resin composition of the present invention comprises a blue pigment (A1), a compound represented by the formula (I), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

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

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

In the present specification, when the compound represented by any formula is capable of forming a tautomer, the compound represented by the formula may be a tautomer thereof, .

≪ Colorant (A) >

In the colored curable resin composition of the present invention, the blue pigment (A1) and the compound represented by the formula (I) are generally included as the colorant (A).

The colored curable resin composition may further contain a blue or violet dye A2 (hereinafter, also referred to as " dye A2 ").

The colored curable resin composition may further contain a dye (Ac) different from the blue pigment (A1) (hereinafter also referred to as "pigment (Ad)") and the blue or purple dye (A2) (Hereinafter sometimes referred to as " dye (Ac) ").

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

≪ Blue pigment (A1) >

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

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

≪ Compound (I) >

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

R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.

X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.

and a represents an integer of 1 to 4.]

However, the compound of formula (I) has a valence of zero.

Examples of the monovalent saturated hydrocarbon group having 3 to 10 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include n-propyl, isopropyl, n-butyl, sec- n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, decyl group, 1-methylbutyl group, 3-methylbutyl group, 4-methylpentyl group, A straight chain or branched chain alkyl group having 3 to 10 carbon atoms such as a methylbutyl group, a 1,5-dimethylhexyl group, a 1,6-dimethylheptyl group, a 2-ethylhexyl group and a 1,1,5,5-tetramethylhexyl group ; A cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and an adamantyl group, and an n-propyl group, an n-butyl group and a 2-ethylhexyl group are preferable Do.

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

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

Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, And an alkoxy group having 1 to 20 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom include a heptafluoropropyl group, a 1,1-difluoropropyl group, a 3,3,3-trifluoropropyl group, a nonafluorobutyl group, A 2,2-difluorobutyl group, an undecafluoropentyl group, a 3- (trifluoromethyl) -3,4,4,4-pentafluorobutyl group, a 6,6,6-trifluorohexyl group Heptachloropropyl group, heptabromopropyl group, 3,3,3-triiodopropyl group, 2,2-dichloro-3,3,3-trifluoropropyl group and the like, and the following formula The indicated group is preferred.

(* Indicates a combined hand.)

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 carbon atoms such as a phenyl group and a naphthyl group; And an aralkyl group having 6 to 10 carbon atoms such as a benzyl group and a phenethyl group, and a phenyl group is preferable.

The aryl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group or n-propyl group; An alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy; A hydroxy group; Or the like.

The substituent of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹³ include a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- , a straight chain alkyl group having 1 to 20 carbon atoms such as an n-nonyl group, an n-decyl group, an n-dodecyl group, an n-hexadecyl group, and an n-icosyl group; Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group, preferably a linear alkyl group having 1 to 5 carbon atoms , More preferably a methyl group or an ethyl group.

X ^+, and Z ⁺ are, each independently _{^{+ N (R 13) 4,}} Na + or K ⁺ denotes _{^{a, + N (R 13) 4}} 4 of R ¹³ in the are may be the same with each other or different. X ⁺ is preferably Na ⁺ or K ⁺ .

Examples of _{^{Z +, -SO 3 - - R}} 51, -SO 3 R ⁵² and R ⁵³ in the ⁺ N (R ¹³⁾ ₄ are preferred.

R ¹ , R ² , R ³ and R ⁴ are each independently preferably an alkyl group having 3 to 10 carbon atoms or a phenyl group which may have a substituent, and is preferably an alkyl group having 3 to 8 carbon atoms or an alkyl group having 1 to 10 carbon atoms More preferably a straight chain alkyl group having 3 to 8 carbon atoms or a phenyl group optionally substituted with an alkyl group having 1 to 3 carbon atoms.

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

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

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

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

Specific examples of the compound (I) include the compounds shown below. In the formula, R ²⁶ represents a 2-ethylhexyl group.

As the compound (I)

The compound represented by the formula (I-1) or the compound represented by the formula (I-20) is preferable,

The compound represented by the formula (I-1) to the compound represented by the formula (I-8), the compound represented by the formula (I-17) or the compound represented by the formula (I-

The compound represented by the formula (I-1) to the compound represented by the formula (I-2), the compound represented by the formula (I-5) or the compound represented by the formula (I-6) are more preferable.

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

≪ Dye (A2) >

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

The blue or violet dye (A2) can be obtained by reacting the xanthene dye (A3), the triarylmethane dye (A4), the tetraazaporphyrin dye (A5), the anthraquinone dye (A6) and the compound represented by the formula And a dye represented by the following formula (A7) (hereinafter sometimes referred to as a dye (A7)), and more preferably at least one dye selected from the group consisting of

(A3), a triarylmethane dye (A4), a dye represented by the formula (A7), and a dye derived from the dye represented by the formula (A7) other than the compound represented by the formula (I) More preferably at least one selected from the group consisting of a polymer containing an alkyl group,

More preferably at least one selected from the group consisting of a triarylmethane dye (A4), a dye represented by the formula (A7), and a polymer comprising a structural unit derived from the dye represented by the formula (A7).

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

The xanthene dye (A3) other than the compound represented by the formula (I) includes a compound having a xanthene skeleton in the molecule, and is a dye different from the compound (I). Preferred examples of the xanthene dye (A3) include a compound represented by the formula (A3-1), a compound represented by the formula (A3-2), a compound represented by the formula (A3-3), and the like. In addition, when the following compounds are anion as a whole, the following compounds represent a part of a state in which a salt is formed together with a counter cation or a counter anion.

(Wherein R ^1C and R ^2C each independently represent a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group which has an ethylenic double bond.

R ^3C and R ^4C is, in the case of each independently represents a group having an alkyl group, or an ethylenic double bond which may have an aryl group, the substituent which may contain a hydrogen atom, a substituent, R ^3C is an alkyl group, in combination with R ^1C When R ^4C is an alkyl group, it may be bonded to R ^2C to form a ring.

R ^5C represents O ^- or OH.

R ^6C and R ^7C is the same or different, O ^-, represents an OH, an alkoxy group, or an amino group.

R ^8C represents an oxygen atom or a sulfur atom.

m and n are the same or different and are 0, 1, 2, or 3, and the sum of m and n is 1 or more and 3 or less.

t is 0 or 1;

R ^9C and R ^10C are the same or different and represent a hydrogen atom or an alkoxy group.

However, the compound of formula (A3-1) is excluded from the compound of formula (A3-2).)

R < ^{1C &} The aryl group of R ^4C includes a phenyl group, a naphthyl group, a benzyl group and the like. Examples of the substituent include an alkyl group such as methyl group and ethyl group; Sulfonic acid group; A sulfonic acid amide group such as a 2-ethylhexylaminosulfoxy group; A sulfonic acid ester group such as a methoxysulfone group; An alkoxy group; Thioalkyl groups; Thioalkoxy groups; And the like. Examples of the aryl group having a substituent include an alkyl-substituted phenyl group such as a tolyl group, a xylyl group, a mesityl group and an ethylphenyl group; A phenyl group, a benzyl group or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to the alkyl group-substituted phenyl group; A phenyl group bonded with an alkoxy group such as an ethoxyphenyl group; A phenyl group, an alkyl group-substituted phenyl group, or a phenyl group, a benzyl group, or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to a phenyl group substituted with an alkyl group, such as a phenyl group bonded with an alkylthio group such as a methylthiophenyl group.

R < ^{1C &} The alkyl group of R ^4C includes straight chain alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n- Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl groups. The substituent includes a phenyl group, a naphthyl group and the like. The substituent may be a sulfonic acid amide group such as a sulfonic acid group or a 2-ethylhexylaminosulfoxy group, a sulfonic acid ester group such as a methoxy sulfoxy group, or the like, and may be included in the phenyl group or the naphthyl group in which they are bonded. Preferably a straight chain alkyl group having 1 to 10 carbon atoms, more preferably a straight chain alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

R < ^{1C &} The group having an ethylenic double bond of R ^4C includes a vinyl group, a (meth) acryloyl group and the like. These vinyl groups, (meth) acryloyl groups and the like may be bonded to alkyl groups, and examples thereof include vinyl-bonded alkyl groups such as allyl group (vinylmethyl group) and vinylethyl group; (Meth) acryloylmethyl group, and (meth) acryloylethyl group. Also, examples of the group in which the (meth) acryloyl group-bonded alkyl group is bonded to the linking group, and the group having the ethylenic double bond. As such a linking group, for example, a group of the following formula can be mentioned.

( ^Wherein R ^11C represents an alkylene group having 1 to 8 carbon atoms such as a methylene group or an ethylene group, * 1 represents a bond to a (meth) acryloyl group-bonded alkyl group, * 2 represents an Represents a combined hand.)

R ^11C is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group.

It is preferable that * 1 is bonded to a (meth) acryloylmethyl group or a (meth) acryloylethyl group.

When R ^1C and R ^3C form a ring or when R ^2C and R ^4C form a ring, the groups R ^1C R ^3C N- * or R (R ^3C ) in the formulas (A3-1) to (A3-3) ^2C R ^4C N- * is, for example, as follows,

Preferably a group represented by the formula (R-5) to a group represented by the formula (R-10)

More preferably a group represented by the formula (R-5), a group represented by the formula (R-6), a group represented by the formula (R-7) and a group represented by the formula (R-9).

^Examples of the alkoxy group of R ^6C , R ^7C , R ^9C and R ^10C include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- And alkoxy groups having 1 to 3 carbon atoms are preferable.

^Examples of the amino group of R ^6C and R ^7C include N-alkylamino groups having 1 to 20 carbon atoms such as N-methylamino group, N-ethylamino group, N- (1-ethylpropyl) amino group and N- (2-ethylhexyl) amino group; N, N-dialkylamino group having 1 to 20 carbon atoms such as N, N-dimethylamino group and N, N-ethylmethylamino group; And N-alkylamino groups having 1 to 10 carbon atoms are preferable, and N-alkylamino groups having 3 to 10 carbon atoms are more preferable.

R ^8C is more preferably a sulfur atom. t is 0 or 1, preferably 0.

R ^9C and R ^10C are preferably one in which one of R ^9C and R ^10C is an alkoxy group and the other is a hydrogen atom.

m and n are the same or different and are preferably 0, 1 or 2, more preferably 0 or 1.

The sum of m and n is preferably 1 or more and 2 or less, and more preferably 1 or less.

The counter cationization includes, for example, those represented by X ⁺ in the formula (I).

Examples of the counter anion include a halide ion, a counter ion represented by the formula (x1) and a formula (x2).

Examples of the halide ion include a fluoride ion, a chloride ion, a bromide ion and an iodide ion.

[In the formula (x1), R ^51x represents an alkyl fluoride group having 1 to 12 carbon atoms.

In formula (x2), R ^52x and R ^53x independently represent a halogen atom or an alkyl fluoride group having 1 to 12 carbon atoms.]

Specific examples of the fluorinated alkyl group having 1 to 12 carbon atoms represented by R ^51x include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 1,1,2,2,2-pentafluoroethyl group, A trifluoromethyl group, a 2-trifluoroethyl group, a 3- (trifluoromethyl) -3,4,4,4-pentafluorobutyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, A perfluorohexyl group, a perfluorohexyl group, and a perfluorohexyl group, and preferably a group having 1 to 12 carbon atoms in which all the hydrogen atoms are substituted with fluorine atoms , More preferably a perfluoroalkyl group of -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , And perfluoroalkyl groups having 1 to 4 carbon atoms such as -CF ₂ CF (CF ₃ ) ₂ and -C (CF ₃ ) ₃ .

The number of carbon atoms of the fluorinated alkyl group represented by R ^51x is preferably 1 to 6, more preferably 1 to 4.

^Examples of the halogen atom represented by R ^52x and R ^53x include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The fluorinated alkyl group having 1 to 12 carbon atoms represented by R ^52x and R ^53x includes the same fluorinated alkyl group represented by R ^51x , preferably a perfluoroalkyl group having 1 to 12 carbon atoms, more preferably Advantageously _{-CF 3, -CF 2 CF 3,} -CF 2 CF 2 CF 3, -CF (CF 3) 2, -CF 2 CF 2 CF 2 CF 3, -CF 2 CF (CF 3) 2, -C (CF _{3) 3,} such as of 1 to 4 carbon atoms may be a perfluoroalkyl group.

R ^52x and R ^53x are, -SO ₂ -N bond to one another ^- may also form a ring containing a - -SO _2.

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

As the xanthene dye (A3)

The compound represented by the formula (1-1) to the compound represented by the formula (1-10), the compound represented by the formula (1-24) to the compound represented by the formula (1-47)

The compound represented by the formula (1-1) to the compound represented by the formula (1-8), the compound represented by the formula (1-24), the compound represented by the formula (1-44) Is more preferable,

The compound represented by formula (1-1), the compound represented by formula (1-8), and the compound represented by formula (1-24) are more preferable.

Examples of the xanthene dyes (A3) include commercially available xanthene dyes (e.g., " Chugai Aminol Fast Pink RH / C ", Daioka Kagaku Kogyo Co., Ltd. " Rhodamin 6G & . It is also possible to synthesize a commercially available xanthene dye as a starting material by referring to Japanese Patent Application Laid-Open No. 2010-32999.

The triarylmethane dye (A4) is a dye containing a compound having a triarylmethane skeleton in its molecule.

Preferable triarylmethane dye (A4) includes a compound represented by formula (A4-1), a compound represented by formula (A4-2), and the like. In addition, when the following compounds are anion as a whole, the following compounds represent part of the form of forming a salt with countercation or counteranion. The counter cationization includes, for example, those represented by X ⁺ in the formula (I). The counter anion includes, for example, counter ions represented by the formulas (x1) and (x2).

( ^Wherein R < ^1D > R ^6D each independently represents a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group which has an ethylenic double bond.

R ^7D, R ^9D each independently represent a hydrogen atom, a methyl group or a fluorine atom.)

R < ^{1D &} The aryl group of R ^6D includes a phenyl group, a naphthyl group, a benzyl group and the like. Examples of the substituent include an alkyl group such as methyl group and ethyl group; Sulfonic acid group; A sulfonic acid amide group such as a 2-ethylhexylaminosulfoxy group; A sulfonic acid ester group such as a methoxysulfone group; An alkoxy group; Thioalkyl groups; Thioalkoxy groups; And the like. Examples of the aryl group having a substituent include an alkyl-substituted phenyl group such as a tolyl group, a xylyl group, a mesityl group and an ethylphenyl group; A phenyl group, a benzyl group or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to the alkyl group-substituted phenyl group; A phenyl group bonded with an alkoxy group such as an ethoxyphenyl group; A phenyl group, an alkyl group-substituted phenyl group, or a phenyl group, a benzyl group, or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to a phenyl group substituted with an alkyl group, such as a phenyl group bonded with an alkylthio group such as a methylthiophenyl group.

R < ^{1D &} The alkyl group of R ^6D includes straight chain alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n- Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl groups. The substituent includes a phenyl group, a naphthyl group and the like. The substituent may be a sulfonic acid amide group such as a sulfonic acid group or a 2-ethylhexylaminosulfoxy group, a sulfonic acid ester group such as a methoxy sulfoxy group, or the like, and may be included in the phenyl group or the naphthyl group in which they are bonded. Preferably a straight chain alkyl group having 1 to 10 carbon atoms, more preferably a straight chain alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

R < ^{1D &} The group having an ethylenic double bond of R ^6D includes a vinyl group, a (meth) acryloyl group and the like. These vinyl groups, (meth) acryloyl groups and the like may be bonded to alkyl groups, and examples thereof include vinyl-bonded alkyl groups such as allyl group (vinylmethyl group) and vinylethyl group; (Meth) acryloylmethyl group, and (meth) acryloylethyl group. Also, examples of the group in which the (meth) acryloyl group-bonded alkyl group is bonded to the linking group, and the group having the ethylenic double bond. As such a linking group, for example, a group of the following formula can be mentioned.

( ^Wherein R ^10D represents an alkylene group having 1 to 8 carbon atoms such as a methylene group or an ethylene group, * 1 represents a bond to a (meth) acryloyl group-bonded alkyl group, * 2 represents an atom bonded to a Represents the combined hand of.

R ^10D is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group.

It is preferable that * 1 is bonded to a (meth) acryloylmethyl group or a (meth) acryloylethyl group.

As the triarylmethane dye (A4), for example,

C. I. Acid violet (hereinafter, abbreviated as C. I. Acid violet, hereinafter referred to only as the description of numbers) 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: , 93, 93: 1, 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269,

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

C. I. Basic Violet 2,

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

C. I. Food Violet 3,

CI Modern Violet 1, 1: 1, 3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, .

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

As the triarylmethane dye (A4)

The compound represented by the formula (4-5), the compound represented by the formula (4-9), the compound represented by the formula (2b-2) to the compound represented by the formula (2b- (2b-15) are preferable, and compounds represented by the formula

The compound represented by the formula (4-5) is more preferable.

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

Preferred tetraazaporphyrin dyes (A5) include compounds represented by the formula (A5-1), compounds represented by the formula (A5-2), and the like. In addition, when the following compounds are anion as a whole, the following compounds represent part of the form of forming a salt with countercation or counteranion. The counter cationization includes, for example, those represented by X ⁺ in the formula (I). The counter anion includes, for example, counter ions represented by the formulas (x1) and (x2).

( ^Wherein R < ^1E > R ^24E represents a group having independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, an amino group, a sulfonic acid group, a sulfonic acid group or an ethylenic double bond.

R ^25E to R ^{32 E} each independently represents a single bond, an oxygen atom or a sulfur atom.

And M < ^1E > represents a metal atom or a metal oxide.

&^Lt; RTI ID = 0.0 & The halogen atom of R ^24E includes a fluorine atom, a chlorine atom, a bromine atom and the like, and a fluorine atom or a chlorine atom is preferable.

&^Lt; RTI ID = 0.0 & The alkyl group of R ^24E includes straight chain alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n- Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl groups. The substituent includes a halogen atom such as a fluorine atom, a hydroxy group, a sulfonic acid group, a sulfonic acid group, an aryl group, an alkyl group-substituted phenyl group, and the like.

&^Lt; RTI ID = 0.0 & The aryl group of R ^24E includes a phenyl group, a naphthyl group, a benzyl group and the like. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom, an alkyl group such as methyl group, ethyl group, propyl group or butyl group, a sulfonic acid group, a 2-ethylhexylaminosulfoxy group, a cyclohexylaminosulfoxy group, A sulfonic acid ester group such as a sulfonic acid amide group and a methoxy sulfoxide group, an alkoxy group, and a thioalkoxy group. Examples of the aryl group having a substituent include an alkyl-substituted phenyl group such as a tolyl group, a xylyl group, a mesityl group and an ethylphenyl group; A phenyl group, a benzyl group or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to the alkyl group-substituted phenyl group; A phenyl group bonded with an alkoxy group such as an ethoxyphenyl group; A phenyl group bonded with an alkylthio group such as a methylthiophenyl group; A phenyl group such as a fluorophenyl group or a chlorophenyl group, a benzyl group or a group in which a halogen atom is bonded to the phenyl group substituted with an alkyl group; A phenyl group, a benzyl group, a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to the phenyl group substituted with an alkyl group, or a phenyl group, a benzyl group or a group in which a halogen atom is bonded to the alkyl group substituted phenyl group .

&^Lt; RTI ID = 0.0 & ^Examples of the amino group of R ^24E include a monoalkylamino group such as a mono-n-butylamino group; Dialkylamino group; A monoarylamino group; A diarylamino group such as a diphenylamino group; A monoaralkylamino group; Diaralkyl amino group; And the like.

&^Lt; RTI ID = 0.0 & The group having an ethylenic double bond of R ^24E includes a vinyl group, a (meth) acryloyl group and the like. These vinyl groups, (meth) acryloyl groups and the like may be bonded to alkyl groups, and examples thereof include vinyl-bonded alkyl groups such as allyl group (vinylmethyl group) and vinylethyl group; (Meth) acryloylmethyl group, and (meth) acryloylethyl group. Also, examples of the group in which the (meth) acryloyl group-bonded alkyl group is bonded to the linking group, and the group having the ethylenic double bond. As such a linking group, for example, a group of the following formula can be mentioned.

( ^Wherein R ^33E represents an alkylene group having 1 to 8 carbon atoms such as a methylene group or an ethylene group, * 1 represents a bond to a (meth) acryloyl group-bonded alkyl group, * 2 represents an atom ≪ / RTI >

R ^33E is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group.

It is preferable that * 1 is bonded to a (meth) acryloylmethyl group or a (meth) acryloylethyl group.

&^Lt; RTI ID = 0.0 & When the alkyl group R ^24E, R ^25E to R ^32E may be an oxygen atom or a sulfur atom, and is preferably an oxygen atom.

M ^1E includes Mg, Cu, Ni, Co, Pd, and VO, and is preferably Cu.

&^Lt; RTI ID = 0.0 & Among R < ^8E &

At least one or more selected from the group consisting of R ^1E , R ^3E , R ^5E and R ^7E is an aryl group which may have a substituent, and at least one or more groups selected from the group consisting of R ^2E , R ^4E , R ^6E and R ^8E Is preferably a hydrogen atom or an alkyl group which may have a substituent,

It is more preferable that all of R ^1E , R ^3E , R ^5E and R ^7E are an aryl group which may have a substituent and R ^2E , R ^4E , R ^6E and R ^8E are both hydrogen atoms or alkyl groups which may have a substituent.

The tetraazaporphyrin dyes include the compounds described below.

The anthraquinone dye (A6) is a dye containing a compound having an anthraquinone skeleton in a molecule. The preferred anthraquinone dye (A6) includes a compound represented by the formula (A6-1).

( ^Wherein R < ^1F > R ^4F each independently represents a hydrogen atom, an aryl group which may have a substituent, an alkyl group which may have a substituent, or a group which has an ethylenic double bond.

R ^5F and R ^6F each independently represent a hydrogen atom, a halogen atom, a nitrile group, a sulfonic acid group or a sulfonic acid group.

R ^1F To The aryl group of R ^4F includes a phenyl group, a naphthyl group, a benzyl group and the like. Examples of the substituent include an alkyl group such as methyl group and ethyl group; A halogen atom such as a fluorine atom or a chlorine atom; Sulfonic acid group; A sulfonic acid amide group such as a 2-ethylhexylaminosulfoxy group, a cyclohexylaminosulfoxy group, and an aminopentylaminosulfoxy group; Sulfonic acid etter groups such as a methoxylation group; An alkoxy group; Thioalkyl groups; Thioalkoxy groups; And the like. Examples of the aryl group having a substituent include an alkyl-substituted phenyl group such as a tolyl group, a xylyl group, a mesityl group and an ethylphenyl group; A phenyl group, a benzyl group or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to the alkyl group-substituted phenyl group; A phenyl group such as a fluorophenyl group or a chlorophenyl group, a benzyl group or a group in which a halogen atom is bonded to the phenyl group substituted with an alkyl group; A phenyl group bonded with an alkoxy group such as an ethoxyphenyl group; A phenyl group, a phenyl group, a benzyl group or a group in which a sulfonic acid group or a sulfonic acid amide group is bonded to the phenyl group substituted with an alkyl group, or a phenyl group, a benzyl group or a benzyl group substituted with an alkylthio group such as a methylthiophenyl group, Is a group in which a halogen atom is bonded to the alkyl group-substituted phenyl group.

Examples of the aryl group which may have a substituent include the substituents described below.

R < ^{1F &} The alkyl group of R ^4F includes straight chain alkyl groups of 1 to 20 carbon atoms such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n- Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl and 2-ethylhexyl groups. The substituent includes a phenyl group, a naphthyl group and the like. The substituent may be a sulfonic acid amide group such as a hydroxy group sulfonic acid group or a 2-ethylhexyl aminosulfoxy group, a sulfonic acid ester group such as a methoxy sulfoxy group or the like, and may be included in the phenyl group or the naphthyl group substituted with a bond thereof. Preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a 1-hydroxyethyl group, Lt; / RTI >

R < ^{1F &} The group having an ethylenic double bond of R ^4F includes a vinyl group, a (meth) acryloyl group and the like. These vinyl groups, (meth) acryloyl groups and the like may be bonded to alkyl groups, and examples thereof include vinyl-bonded alkyl groups such as allyl group (vinylmethyl group) and vinylethyl group; (Meth) acryloylmethyl group, and (meth) acryloylethyl group. Also, examples of the group in which the (meth) acryloyl group-bonded alkyl group is bonded to the linking group, and the group having the ethylenic double bond. As such a linking group, for example, a group of the following formula can be mentioned.

( ^Wherein R ^7F represents an alkylene group having 1 to 8 carbon atoms such as a methylene group and an ethylene group).

* 1 represents a bond with a (meth) acryloyl group-bonded alkyl group, and * 2 represents a bond with a N atom.

R ^7F is preferably an alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group.

It is preferable that * 1 is bonded to a (meth) acryloylmethyl group or a (meth) acryloylethyl group.

As the anthraquinone dye (A6), for example,

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

CI Solvent Blue 12, 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105 , 111, 112, 122, 128, 132, 136, 139,

C. I. Acid Violet 34,

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

C. I. Disperse Violet 26, 27,

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

C. I. Direct Blue 40,

C. I. Modern Blue 8 and the like.

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

As the anthraquinone dye (A6)

A compound represented by the formula (3-11) or a compound represented by the formula (3-12) is preferable.

In the present specification, the dye represented by the formula (A7) is a concept including a tautomer of the compound represented by the formula (A7).

[In the formula (A7)

g represents an arbitrary natural number.

G ^{g -} represents anion of g.

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

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

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

^Examples of the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include methyl group, ethyl group, n-propyl group, isopropyl group, A cyclopropyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexyl group, Cyclohexyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, decahydronaphthyl group, adamantyl group, 2-alkyladamantan-2-yl group, 1 Alkyl groups having 1 to 20 carbon atoms such as - (adamantan-1-yl) alkan-1-yl group, norbornyl group, methylnorbornyl group and isobornyl group. Preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

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

Specific examples of the group in which -CH ₂ - contained in the alkyl group represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are substituted with -O- The same can be said. Is preferably a group in which -CH ₂ - contained in an alkyl group having 1 to 10 carbon atoms is substituted with -O-, more preferably, -CH ₂ - included in an alkyl group having 1 to 6 carbon atoms is -O- Lt; / RTI >

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

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

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

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

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert- A cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a cycloheptyl group, a cyclohexyl group, a cyclohexyl group, a cyclohexyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, A cyclohexyl group, an octyl group, a cyclononyl group, a cyclodecyl group, a decahydronaphthyl group, an adamantyl group, a 2-alkyladamantan-2-yl group, a 1- (adamantan- An alkyl group having 1 to 20 carbon atoms such as a methyl group, a norbornyl group, a methyl norbornyl group and an isobornyl group. -CH ₂ other than the - - -CH ₂ adjacent to the nitrogen atom contained in these alkyl groups, being optionally substituted by a -O-, The substituent is an alkyl group which may have the art, an amino group, substituted amino group, a halogen atom and a silicon atom And the like.

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

Examples of the substituted amino group include groups having 1 to 8 carbon atoms such as methylamino, ethylamino, propylamino, isopropylamino, butylamino, sec-butylamino, tert- butylamino, An alkylamino group and a dialkylamino group having 1 to 8 carbon atoms.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

R ⁵⁶ represents an optionally substituted amino group.

* Represents the bonding bond with the carbon atom.]

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

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

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

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

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

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

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

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

G ^{g -} is preferably a monovalent anion, and for example, a fluoride ion, chloride ion, bromide ion, and not indicated by the halide ions, formula (y1) such as iodide ions on the formula (y2) Anion represented by formula (y3) and anion represented by formula (y3).

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

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

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

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, An octyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a methylcyclohexyl group.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The blue or violet dye may be a monomer or a polymer. The polymer which is a blue or purple dye is a polymer containing a structural unit derived from a blue or purple dye and may be a polymer consisting only of a structural unit derived from a blue or purple dye and may be a polymer different from a structural unit derived from a blue or purple dye (Hereinafter may be referred to as copolymer (a) in some cases).

The structural unit derived from the blue or purple dye may have a divalent or higher group derived from a blue or purple dye and may have a monovalent group derived from a blue or purple dye. The group derived from the blue or purple dye may have anion or cation.

Examples of the copolymer (a) include a copolymer containing at least one selected from the group consisting of structural units represented by the following formulas (1) to (3) in addition to structural units derived from a blue or violet dye .

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

[In the formula (1), R ⁹ and R ¹⁰ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, Alkylaryl groups or combinations thereof.

and m 'represents an integer of 0 to 5.]

[In the formula (2), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an alkylaryl group which may have a substituent, Combination.

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

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

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

R ¹⁵ represents -COOH or -CONHR ¹⁸ .

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

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

The structural unit other than the structural unit derived from the blue or violet dye is an ethylenic unsaturated monomer containing at least one carboxyl group, and specific examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid and fumaric acid.

The weight ratio of the ethylenically unsaturated monomer containing at least one carboxyl group is usually 1 to 50% by weight, preferably 3 to 40% by weight, based on the total weight of the monomers forming the copolymer (a) Preferably 5 to 30% by weight.

Specific examples thereof include an alkenyl aromatic monomer such as styrene,? -Methylstyrene, vinyltoluene and vinylbenzyl methyl ether; and a structural unit (Z) derived from a monomer other than the above-mentioned monomers.

Acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Unsaturated carboxylic acid ester compounds such as 2-hydroxybutyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate;

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

Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate;

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

Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;

Unsaturated amide compounds such as acrylamide and methacrylamide;

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

As the structural unit (Z), an unsaturated carboxylic acid ester compound, a dicarbonylimide derivative, and a combination thereof are preferable,

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, More preferably,

Methyl acrylate, methyl methacrylate, benzyl acrylate, benzyl methacrylate, N-benzyl maleimide, and combinations thereof.

When the unsaturated carboxylic acid ester compound and the dicarbonylimide derivative are combined, the molar ratio thereof (unsaturated carboxylic acid ester compound: dicarbonylimide derivative) is preferably 97: 3 to 3:97, more preferably 93: 7 To 50:50, and more preferably 90:10 to 60:40.

The structural unit derived from the blue or violet dye contained in the copolymer (a) is preferably a structural unit derived from a blue or purple dye containing a group having an ethylenic double bond, and a structural unit derived from a xanthine dyestuff (A3) A structural unit derived from a triarylmethane dye (A4), a structural unit derived from a triarylmethane dye (A4), and a structural unit derived from a dye represented by the formula (A7) , A structural unit derived from a dye represented by the formula (A7), and a structural unit derived from a dye represented by the formula (A7).

Examples of the structural unit derived from the xanthene dye (A3) include a structural unit derived from a compound represented by the formula (1-45) containing a group having an ethylenic double bond or a compound represented by the formula (1-47) .

Examples of the structural unit derived from the triarylmethane dye (A4) include structural units derived from a compound represented by the formula (2b-1) containing a group having an ethylenic double bond or a compound represented by the formula (2b-19) Unit is preferable.

The structural unit derived from the dye represented by the formula (A7) is preferably a dye represented by the formula (A7) wherein R ^21A or R ^22A is an amino group substituted with a group containing an acryloyl group or a methacryloyl group, More preferably a structural unit derived from a compound represented by the formula (A-I-a15).

In the copolymer (a), the ratio of the respective structural units derived from the respective structural units in the copolymer (a)

A structural unit derived from an ethylenically unsaturated monomer containing at least one carboxyl group (concretely acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid); 20 to 50% by mole (preferably 25 to 45% by mole)

A structural unit derived from a blue or violet dye; 0.1 to 25 mol% (preferably 0.5 to 20 mol%)

A structural unit (Z); 25 to 79.9 mol% (preferably 35 to 74.5 mol%),

.

The content of the dye (A2) is usually 80 to 10000 parts by mass, preferably 80 to 7500 parts by mass, more preferably 80 to 1000 parts by mass, per 100 parts by mass of the compound (I) Is 80 to 600 parts by mass, and more preferably 80 to 300 parts by mass.

≪ Dye (Ac) and Pigment (Ad) >

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

As the pigment (Ad), a known pigment can be used without particular limitation, and for example, a pigment classified by pigment in the color index (The Society of Dyers and Colourists) is cited.

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

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

(1) The blue pigment (A1), the compound (I) and the blue or purple dye (A2)

(2) A blue pigment (A1), a compound (I), and a triarylmethane dye (A4)

(3) at least one member selected from the group consisting of a dye containing a blue pigment (A1), a compound (I) and a dye represented by the formula (A7) and a polymer containing a constituent unit derived from the dye represented by the formula Species dyes

(4) The blue pigment (A1), the compound (I), the blue or purple dye (A2) and the violet pigment (Ad)

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

≪ Resin (B) >

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

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

(Hereinafter referred to as " (c) ") of the resin (K2) (a) and the monomer (b) copolymerizable with the monomer (a) );

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

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

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

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

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

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

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

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , Unsaturated dicarboxylic anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

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

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

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

(b) is a polymer having, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) Compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

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

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)") and the like.

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

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

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl Acrylate (for example, cyclomer A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (e.g., A compound represented by the formula (I) and a compound represented by the formula (II).

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

X ^a and X ^b represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

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

* Stands for a binding hand with O.]

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

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

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

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

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

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

Examples of the compound represented by the formula (II) include compounds represented by the formulas (II-1) to (II-15). (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II- ). ≪ / RTI > More preferred are compounds represented by formula (II-1), formula (II-7), 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 alone. In addition, they can be mixed at an arbitrary ratio. When mixing, the mixing ratio thereof is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and even more preferably 20: 80 to 80:20.

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

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

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

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

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

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

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

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

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

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

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

(a); 2 to 60 mol%

(b); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(b); 50 to 90 mol%

Is more preferable.

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

Resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by the Chemical Society of Japan, 1st Ed., 1st Ed., March 1, 1972, Takatsuki Otsu) . ≪ / RTI >

Specifically, a predetermined amount of the components (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel, for example, by replacing oxygen by nitrogen, and heating and keeping the mixture in a deoxidizing atmosphere . The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (such as benzoyl peroxide) As the solvent, any one that dissolves the respective monomers may be used. As the solvent (E) of the colored curable resin composition of the present invention, there may be mentioned a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention, The manufacturing process of the composition can be simplified.

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

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c); 1 to 65 mol%

, ≪ / RTI >

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c); 5 to 60 mol%

Is more preferable.

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

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

In the resin [K3], the ratio of the structural units derived from each other is preferably such that, among all structural units constituting the resin [K3]

(a); 2 to 60 mol%

(c); 40 to 98 mol%

, ≪ / RTI >

(a); 10 to 50 mol%

(c); 50 to 90 mol%

Is more preferable.

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

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

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

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

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

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

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

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

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

the proportion of the structural units derived from the structural units (b) and (c) is preferably such that the total number of moles of the structural units constituting the above-

(b); 5 to 95 mol%

(c); 5 to 95 mol%

, ≪ / RTI >

(b); 10 to 90 mol%

(c); 10 to 90 mol%

Is more preferable.

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

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

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

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / ) Resin [K1] such as an acrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2,6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymers, etc. Of resin [K2]; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin such as a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride in addition to the resin [K6] have.

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

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 35,000 and 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution of the coloring pattern tends to be improved.

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

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

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

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of being polymerized by an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenic unsaturated bond, Is a (meth) acrylic acid ester compound.

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

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

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

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

≪ Polymerization initiator (D) >

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

As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and imidazole compounds is preferable, and O- A polymerization initiator comprising an acyloxime compound is more preferable.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Carbamoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- 3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. O-acyloxime compounds were prepared by the same method as in Example 1 except that N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, Oxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable. If these O-acyloxime compounds are used, color filters of high brightness tend to be obtained.

The alkylphenone compound may be at least one selected from the group consisting of 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- Butan-1-one, 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone , Oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyl dimethyl ketal. IRGACURE 369, 907, 379 (manufactured by BASF Co., Ltd.) and the like may be used.

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

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

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373), 2 Bis (2-chlorophenyl) -4,4 ', 5,5' -tetraphenylbiimidazole, 2,2'-bis -Tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Patent Laid- (See, for example, Japanese Unexamined Patent Application Publication No. 7-10913, etc.) in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group .

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator (D1) (particularly, amines) described below.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyl And onium salts such as iodonium hexafluoroantimonate, nitrobenzyltosylates, benzoin tosylates, and the like.

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

≪ Polymerization initiator (D1) >

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

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

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylamino benzoic acid 2 Diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone) -Bis (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

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

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

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

When the polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Wealth. When the amount of the polymerization initiator (D1) is within this range, it is possible to form a colored pattern with higher sensitivity, and the productivity of the color filter tends to be improved.

≪ Solvent (E) >

The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- and no -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole .

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

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

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

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

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

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 占 폚 or more and 180 占 폚 or less at 1 atm is preferable from the viewpoint of coatability and drying property. Examples of the solvent include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-methyl-2-pentanone and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

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

≪ Leveling agent (F) >

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

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specific examples thereof include Toray silicon DC3PA, copper (SH7PA), copper DC11PA, copper (copper) SH21PA, copper (copper) SH29PA, copper (copper) SH30PA, copper (copper) SH8400 (trade names: manufactured by Toray Dow Corning), KP321, KP322, KP323, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (produced by Momentive Performance Materials Japan Joint-Industrial Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples thereof include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554 (Manufactured by Mitsubishi Materials Electronics Co., Ltd.), RS-718-K (manufactured by DIC Corporation), FTOP (registered trademark) EF301, EF303, EF351, Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

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

The content of the leveling agent (F) is preferably 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.01 mass% or less, Mass% to not more than 0.05 mass%. When the content of the leveling agent (F) is in the above range, the flatness of the color filter can be improved.

≪ Other components >

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

≪ Process for producing colored curable resin composition >

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

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

The blue pigment (A1) is preferably mixed with a part 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 becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended.

As the pigment dispersant, a commercially available surfactant can be used and a surfactant such as silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, . Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like (Manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyoeisha Chemical Co., Ltd.), Solfus (manufactured by Zeneca), EFKA (manufactured by BASF Japan Co., Ltd.) (Registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by BICKEMIS Co., Ltd.). These may be used alone or in combination of two or more kinds.

The desired colored curable resin composition can be prepared by mixing the remaining components in the thus obtained pigment dispersion to a predetermined concentration.

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

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

[Example]

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by examples. In the examples, "% " and " part (s) "

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

[Synthesis Example 1]

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

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

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

                          Exact Mass: 602.2

[Synthesis Example 2]

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

[Synthesis Example 3]

The following reaction was carried out in a nitrogen atmosphere. 36.3 parts of potassium thiocyanate and 160.0 parts of acetone were put into a flask equipped with a condenser and a stirrer, followed by stirring at room temperature for 30 minutes. Subsequently, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, the reaction mixture was ice-cooled (ice-cooled), and 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Subsequently, after ice-cooling the reaction mixture, 34.2 parts of 30% sodium hydroxide aqueous solution was added dropwise. After completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Subsequently, 35.3 parts of chloroacetic acid at room temperature was added dropwise. After completion of dropwise addition, the mixture was stirred for 7 hours under reflux. Subsequently, the reaction mixture was allowed to cool to room temperature, and then the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was further added, and the mixture was stirred for 30 minutes. Subsequently, stirring was stopped, and the mixture was allowed to stand for 30 minutes, and the organic layer and the aqueous layer were separated. After the aqueous layer was discarded by separating operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of sodium sulfate was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation using a diverter to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 캜 to obtain 52.0 parts of a compound represented by the formula (B-I-1). Yield 50%

The following reaction was carried out in a nitrogen atmosphere. 9.3 parts of the compound represented by the formula (B-I-1) and 10.0 parts of 4,4'-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a flask equipped with a stirrer, And 20.0 parts of toluene were added. Then, 14.8 parts of phosphorus oxychloride was added, followed by stirring at 95 to 100 ° C for 3 hours. The reaction mixture was then cooled to room temperature and then diluted with 170.0 parts of isopropanol. Subsequently, the diluted reaction solution was poured into 300.0 parts of saturated saline, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Subsequently, stirring was stopped, and the mixture was allowed to stand for 30 minutes, and the organic layer and the aqueous layer were separated. After the water layer was discarded by separating operation, the organic layer was washed with 300 parts of saturated saline. An appropriate amount of gum was added to the organic layer, followed by stirring for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation using a diverter to obtain a blue-violet solid. Further, the violet solid was dried under reduced pressure at 60 캜 to obtain 19.8 parts of a compound represented by the formula (A-I-a1). Yield 100%

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

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

                          Exact Mass: 636.3

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

[Synthetic Example 4]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, and 305 parts of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 46 parts of acrylic acid and 0.4 part of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (I-1) and the compound represented by formula (II-1) 50:50) was dissolved in 185 parts of ethyl lactate to prepare a solution. The resulting solution was dropped into a flask kept at 70 캜 for 4 hours by using a dropping funnel.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was added dropwise to the flask over 4 hours using a separate dropping funnel. After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70 占 폚 for 4 hours and then cooled to room temperature. The weight average molecular weight (Mw) was 9.1 占⁰³ , the molecular weight distribution was 2.1, the solid content was 26% To obtain a resin B1 solution having a solid acid value of 120 mg-KOH / g. Resin B1 has a structural unit shown below.

[Synthetic Example 5]

182 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and the atmosphere in the flask was changed from nitrogen to air. After raising the temperature to 100 DEG C, To a mixture of 70.5 parts of acrylate, 43.0 parts of methacrylic acid, 22.0 parts of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and 136 parts of propylene glycol monomethyl ether acetate was added 2,2'- And 3.6 parts of azobisisobutyronitrile was added dropwise, followed by further stirring at 100 占 폚.

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

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

Device; K2479 (manufactured by Shimadzu Corporation)

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION)

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

[Synthetic Example 6]

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

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

[Synthetic Example 7]

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

[Synthetic Example 8]

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

[Synthesis Example 9]

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

[Synthesis Example 10]

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

[Synthesis Example 11]

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

[Synthesis Example 12]

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

[Synthetic Example 13]

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

[Synthesis Example 14]

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

[Synthesis Example 15-18]

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

[Synthesis Examples 19-22]

The compound represented by the formula (aa8), benzyl methacrylate, methacrylic acid, methyl methacrylate and N-benzyl maleimide were respectively fed into the flask equipped with a cooling tube and a stirrer under the weights shown in Table 2 below, As the initiator, 2,2'-azobis (2,4-dimethylvaleronitrile was added in an amount of 6 parts by weight based on 100 parts by weight of the total amount of the compound. Then, relative to 100 parts by weight of the total amount of the initiator and the compound, , 300 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added thereto, and stirring was started slowly under a nitrogen atmosphere. The reaction solution was heated to 90 占 폚 and stirred for 10 hours to obtain a copolymer solution.

[Synthesis Examples 23-26]

A copolymer solution is obtained in the same manner as in Synthesis Examples 19 to 22, except that a compound represented by the formula (aa9) is used instead of the compound represented by the formula (aa8).

[Synthesis Examples 27-30]

A copolymer solution is obtained in the same manner as in Synthesis Examples 19 to 22, except that a compound represented by the formula (aa10) is used instead of the compound represented by the formula (aa8).

[Synthesis Examples 31-42]

3.5 wt% of each copolymer solution prepared in Synthesis Example 19-30, 12 wt% of CI Pigment Blue Pigment 15: 6 (BASF), 6 wt% of dispersing agent (BYK, Diperbyk 6919) and propylene glycol monomethyl ether 78.5% by weight of acetate are mixed and dispersed using a paint shaker for 24 hours to prepare respective copolymer dispersions 1 to 12.

[Synthesis Example 43]

To the reactor were added 25 parts of pararosaniline hydrochloride and 500 parts of ethanol, and the mixture was stirred at 200 占 폚 for 8 hours. The temperature of the solution is then lowered to 25 DEG C and 174 parts of 2-methyl-2-propene-carboxyoxyethyl ester is slowly added dropwise to the solution for 5 hours. Subsequently, the temperature of the solution was raised to 70 캜 and stirred for 24 hours. After completion of the reaction, the reaction product was slowly recrystallized in ethanol to obtain 54.5 parts of a compound represented by the formula (aa11).

[Synthesis Example 44]

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

Subsequently, the temperature is lowered to 25 DEG C, and 209 parts of 2-methyl-2-propene-sulfaminoethylester is slowly added dropwise to the solution for 5 hours. Subsequently, the temperature of the solution was raised to 70 캜 and stirred for 24 hours. After the reaction was completed, the reaction solution was slowly recrystallized from ethanol to obtain 58.2 parts of a compound represented by the formula (aa12).

[Synthesis Example 45]

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

[Synthesis Examples 46-49]

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

[Synthesis Examples 50-53]

3.5 wt% of each of the copolymer solutions prepared in Synthesis Examples 46-49, 12 wt% of CI Pigment Blue Pigment 15: 6 (BASF), 6 wt% of dispersing agent (BYK, Diperbyk 6919) and propylene glycol monomethyl ether 78.5% by weight of acetate are mixed and dispersed using a paint shaker for 24 hours to prepare copolymer dispersions 50 to 53, respectively.

[Synthesis Example 54]

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

[Example 1]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      1.5 parts

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 2]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 3]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.3 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 4]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.8 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 5]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      1.1 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 6]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.3 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Comparative Example 1]

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

Acrylic pigment dispersant      3.9 part

Propylene glycol monomethyl ether acetate      130 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01, 10 copies

(E) Solvent: Ethyl lactate      556 part

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

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

Were mixed to obtain a colored curable resin composition.

≪ Preparation of colored pattern >

The colored curable resin composition was coated on a 5 cm square glass substrate (Eagle 2000; Corning) by spin coating, and then prebaked at 100 占 폚 for 3 minutes to obtain a colored layer. After cooling down, the distance between the substrate on which the colored layer was formed and the quartz glass photomask was set to 100 mu m and an exposure amount (365 nm (nm)) of 150 mJ / Standard). As the photomask, a 100 μm line and space pattern was formed. The colored layer after light irradiation was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 DEG C for 60 seconds, washed with water, post baked in an oven at 200 DEG C for 30 minutes, A colored pattern was obtained.

≪ Measurement of film thickness &

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

[Evaluation of color]

Spectroscopy was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation), and the xy chromaticity coordinates (x, y) in the XYZ color system of CIE were measured using the characteristic function of the C light source ) And three stimulus values Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Tables 6 and 7.

[Heat resistance evaluation]

The coated film of the obtained colored curable resin composition was heated at 230 占 폚 for 20 minutes and the color difference? Eab * before and after heating of the coated film was measured using a colorimeter (OSP-SP-200; manufactured by Olympus). As a result of evaluating the heat resistance of the obtained coating film, the color difference (? Eab *) is shown in Tables 6 and 7. The smaller the? Eab *, the smaller the color change before and after heating, and the better the heat resistance.

[Example 7]

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 xanthene dye 1.

[Example 8]

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

[Example 9]

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

[Example 10]

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

[Example 11]

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

[Example 12]

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

[Example 13]

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

[Example 14]

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

[Example 15]

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

Acrylic pigment dispersant     0.5 part

Propylene glycol monomethyl ether acetate      30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)     0.1 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,      10 copies

(E) Solvent: Ethyl lactate     556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 16]

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

Acrylic pigment dispersant     0.5 part

Propylene glycol monomethyl ether acetate      30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)     0.1 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,      10 copies

(E) Solvent: Ethyl lactate     556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 17]

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

Acrylic pigment dispersant     0.5 part

Propylene glycol monomethyl ether acetate      30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)    0.08 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,      10 copies

(E) Solvent: Ethyl lactate     556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 18]

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

Acrylic pigment dispersant     0.5 part

Propylene glycol monomethyl ether acetate      30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)     0.1 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,      10 copies

(E) Solvent: Ethyl lactate     556 part

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

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

Were mixed to obtain a colored curable resin composition.

Each of the colored curable resin compositions obtained in Examples 15 to 18 was subjected to chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 5. The results are shown in Table 8. The larger the value of Y, the higher the brightness. The smaller the value of? Eab *, the smaller the change in color before and after heating and the better the heat resistance.

[Example 19]

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

[Example 20]

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

[Example 21]

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

[Example 22]

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

[Example 23]

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

[Example 24]

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

[Example 25]

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

[Example 26]

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

[Example 27]

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

[Example 28]

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

[Example 29]

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

[Example 30]

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

[Example 31]

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

[Example 32]

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

[Example 33]

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

[Example 34]

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

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.03 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,  10 copies

(E) Solvent: Ethyl lactate 556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 35]

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

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.04 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,  10 copies

(E) Solvent: Ethyl lactate 556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 36]

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

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.04 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,  10 copies

(E) Solvent: Ethyl lactate 556 part

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

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

Were mixed to obtain a colored curable resin composition.

[Example 37]

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

Acrylic pigment dispersant 0.2 part

Propylene glycol monomethyl ether acetate  30 copies

And the pigment is sufficiently dispersed by using a bead mill, and subsequently,

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

(A) Colorant: A compound represented by the formula (I-2)      0.05 part

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

(C) Polymerizable compound: dipentaerythritol hexaacrylate

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

(D) A polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01,  10 copies

(E) Solvent: Ethyl lactate 556 part

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

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

Were mixed to obtain a colored curable resin composition.

Each of the colored curable resin compositions obtained in Examples 34 to 37 was subjected to chromaticity evaluation and heat resistance evaluation in the same manner as in Examples 1 to 5. The results are shown in Table 9. The larger the value of Y, the higher the brightness. The smaller the value of? Eab *, the smaller the change in color before and after heating and the better the heat resistance.

[Example 38]

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

[Example 39]

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

[Example 40]

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

[Example 41]

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

[Example 42]

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

[Example 43]

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

[Example 44]

A colored curable resin composition was obtained in the same manner as in Example 1, except that the compound represented by the formula (4-9) was used in place of the xanthene dye 1, and further that C.I. Pigment Violet 23 was contained.

[Example 45]

A colored curable resin composition is obtained in the same manner as in Example 1, except that the compound represented by the formula (1-44) is used instead of the xanthene dye 1, and further the colorant contains C. I. Pigment Violet 23.

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

Claims (10)

A colored curable resin composition comprising a blue pigment (A1), a compound represented by the following formula (I), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

[In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent.
R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.
X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.
and a represents an integer of 1 to 4.] The method according to claim 1,
Further comprising a blue or violet dye (A2). The method according to claim 1,
The blue pigment (A1) is CI Pigment Blue 15: 6. 3. The method of claim 2,
The blue or violet dye (A2)
The xanthene dyes (A3) other than the compound represented by the formula (I)
Triarylmethane dyes (A4),
Formula (A7):

[In the formula (A7)
g represents an arbitrary natural number.
G ^g- represents anion of g.
D represents a heteroaromatic hydrocarbon group which may have a substituent.
^{R 1A, R 2A, R 3A} , R 4A, R 5A, R 6A, R 7A and R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an alkyl group, -CH contained in these groups ₂ - may be substituted with -O-.
R ^21A and R ^22A each independently represent an amino group which may be substituted.]
A dye represented by the general formula
A polymer comprising a structural unit derived from the dye represented by the above formula (A7)
At least one coloring curable resin composition. 5. The method of claim 4,
The blue or violet dye (A2)
Triarylmethane dyes (A4),
A dye represented by the formula (A7)
A polymer comprising a structural unit derived from the dye represented by the above formula (A7)
At least one coloring curable resin composition. Wherein the triarylmethane dye (A4) is a polymer, wherein the coloring agent comprises a compound represented by Formula (A4), a triarylmethane dye (A4), a blue pigment (A1) and a compound represented by Formula (I).

[In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent.
R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.
X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.
and a represents an integer of 1 to 4.] The formula (A7)

[In the formula (A7)
g represents an arbitrary natural number.
G ^g- represents anion of g.
D represents a heteroaromatic hydrocarbon group which may have a substituent.
^{R 1A, R 2A, R 3A} , R 4A, R 5A, R 6A, R 7A and R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxy group or an alkyl group, -CH contained in these groups ₂ - may be substituted with -O-.
R ^21A and R ^22A each independently represent an optionally substituted amino group, and a polymer containing a constituent unit derived from the dye represented by the formula (A7) A dye of the species,
A blue pigment A1,
Formula (I):

[In the formula (I), R ¹ , R ² , R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 3 to 10 carbon atoms which may have a substituent or an aryl group which may have a substituent.
R ^51, R ⁵² and R ⁵³ are each independently a hydrogen atom, -SO ₃ ^-, -SO ₃ H or -SO ₃ ^- Z ⁺ represents a.
X ^+, and Z ⁺ are each independently selected from N ⁺ (R ¹³⁾ _4, Na ⁺ or K ⁺ denotes a, R ¹³ is, represents a saturated monovalent hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ⁺ N (R ¹³⁾ _{4 4} of R ¹³ in the are may be the same or different from each other.
and a represents an integer of from 1 to 4. 2. The colorant according to claim 1, 8. The method according to claim 6 or 7,
The blue pigment (A1) is CI Pigment Blue 15: 6. A color filter formed from the colored curable resin composition according to any one of claims 1 to 5. A display device comprising the color filter according to claim 9.