KR20170074179A - The compound, colored curable resin composition, color filter and liquid crystal display device - Google Patents

Abstract

(A) having a cation and an anion in a molecule, an anion (b) containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, and an alkaline earth metal (C), a colored curable resin composition containing the same, a color filter manufactured therefrom, and a liquid crystal display device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a coloring and curing resin composition,

TECHNICAL FIELD The present invention relates to a compound comprising a cation and an anion in a molecule, a cation, and an anion, a colored curable resin composition using the same, a color filter, and a liquid crystal display.

A coating film formed from a colored curable resin composition is desired to have excellent heat resistance, and various techniques for improving heat resistance and the like have been developed.

Patent Document 1 describes a colored curable resin composition comprising a triarylmethane-based basic dye and a salt-forming compound composed of the counter compound.

Japanese Laid-Open Patent Publication No. 2014-170098

In the prior art, it is disclosed that a salt-forming compound is disclosed in terms of improving desired characteristics. However, the use of a compound having both a cation and an anion in a molecule as a heat-resistant compound is not taught in the patent literature (Japanese Patent Laid- 170098).

Accordingly, an object of the present invention is to provide a colored curable resin composition capable of forming a coating film having good heat resistance and a compound used in the colored curable resin composition.

In order to achieve the above object,

The present invention relates to a compound (a) having a cation and an anion in a molecule,

(B) having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, and

And a cation (c) containing an alkaline earth metal.

In one embodiment of the present invention, the compound (a) is a xanthene compound (a1).

In one embodiment of the present invention, the xanthene compound (a1) is a compound represented by the formula (a1-1).

[Chemical Formula 1]

[In formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -N (R ¹⁰ ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- Or -NHCO-. ≪ / RTI > However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.

R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ together may form a ring containing a nitrogen atom.

R ⁵ and R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

In one embodiment of the present invention, there is provided a compound wherein the cation (c) is at least one member selected from the group consisting of a magnesium cation, a calcium cation, a strontium cation and a barium cation.

The present invention also provides a colored curable resin composition comprising the compound of the present invention, a resin, a polymerizable compound and a polymerization initiator.

The present invention also provides a color filter formed from the colored curable resin composition of the present invention.

The present invention also provides a liquid crystal display device having the color filter of the present invention.

According to the present invention, it is possible to provide a colored curable resin composition which can be a coating film having improved heat resistance and a compound used therefor.

Hereinafter, the present invention will be described in more detail.

1. Compound

The compound of the present invention includes at least one element selected from the group consisting of a compound (a) having a cation and an anion in the molecule (hereinafter sometimes referred to as a compound (a)), tungsten, molybdenum, An anion (b) as an essential element, and a cation (c) containing an alkaline earth metal.

1-1. The compound (a)

Compound (a) has a cation and an anion in the molecule. The cation and the anion in the molecule may have the same charge number or different charge numbers, and it is preferable that the cation and the anion have the same charge number in the molecule. More preferably, it has a cation and an anion in the molecule in the same charge number of not less than 1 but not more than 5, more preferably a cation and an anion in the molecule in the same charge number of not less than 1 but not more than 3, And anions as one charge number.

The compound (a) is preferably a xanthene compound (a1) or a squarylium compound (a2).

1-1-1. Xanthene compound

As the xanthene compound (a1), a compound represented by the formula (a1-1) (hereinafter sometimes referred to as a " compound (a1) ") is preferred. The compound (a1) may be a tautomer thereof.

 (2)

[In formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -N (R ¹⁰ ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- Or -NHCO-. ≪ / RTI > However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.

R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ together may form a ring containing a nitrogen atom.

R ⁵ and R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ and R ¹⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, , A straight chain alkyl group such as a dodecyl group, a hexadecyl group and an icosyl group; Branched chain alkyl groups such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group. The saturated hydrocarbon groups represented by R ¹ to R ⁴ and R ¹⁰ preferably have 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.

The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -N (R ¹⁰ ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- Or -NHCO-. ≪ / RTI > However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -O- include the following (* represents a bonding position).

(3)

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -CO- include the following (* represents a bonding position).

[Chemical Formula 4]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -NR ¹⁰ - include the following (* represents a bonding position).

[Chemical Formula 5]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -OCO- include the following (* represents the bonding position).

[Chemical Formula 6]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -COO- include the following (* represents the bonding position).

(7)

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -OCONH- include the following (* represents the bonding position).

[Chemical Formula 8]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -NHCOO- include the following (* represents a bonding position).

[Chemical Formula 9]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -CONH- include the following (* represents the bonding position).

[Chemical formula 10]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is substituted with -NHCO- include the following (* represents a bonding position).

(11)

Examples of the substituent which the saturated hydrocarbon group represented by R ¹ to R ⁴ may have include an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group.

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

Examples of the ring formed by R ¹ and R ² together and the ring formed by R ³ and R ⁴ together include the following.

[Chemical Formula 12]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group.

The aromatic hydrocarbon group having 6 to 10 carbon atoms may have a substituent. As the substituent group which may have the aromatic hydrocarbon is a halogen ^{atom, -R 7, -OH, -OR 7} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R ⁷ , -SR ⁷ , -SO ₂ R ⁷ , -SO ₃ R ⁷ and -SO ₂ N (R ⁸ ) (R ⁹ ).

R ⁷ represents an alkyl group having 1 to 10 carbon atoms which may have a halogen atom. The methylene group contained in the alkyl group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group or -N (R ⁷ ) -. However, the adjacent methylene group is not simultaneously substituted with the same group, and the terminal methylene group is not substituted.

R ⁸ and R ⁹ independently represent a saturated hydrocarbon group or a hydrogen atom of 1 to 10 carbon atoms which may be substituted with a hydroxy group or a halogen atom.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and heptyl group.

Examples of -OR ⁷ include alkylox such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy Time and so on.

Examples of -CO ₂ R ⁷ include alkyloxycarbonyl groups such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group.

Examples of -SR ⁷ include an alkylsulfanyl group such as a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

Examples of -SO ₂ R ⁷ include alkylsulfonyl groups such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.

Examples of -SO ₃ R ⁷ include alkyloxonylphenyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butyloxycarbonyl group, a hexyloxyl group, And the like.

Group ^{_{-SO 2 N (R 8) (}} R 9) roneun for example sulfamoyl;

N-ethylsulfamoyl group, N-ethylsulfamoyl group, N-ethylsulfamoyl group, N-isopropylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N- isobutylsulfamoyl group, N-sec- (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, an N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1 substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;

An N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-ethylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group and the like.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁵ and R ⁶ include methyl, ethyl, propyl, butyl, isobutyl, isopentyl and pentyl groups. Among them, R ⁵ and R ⁶ are preferably hydrogen atoms.

R ⁸ and R ⁹ , independently of each other, may represent a nitrogen heterocycle having from 3 to 10 members, together with the nitrogen atom. Examples of the heterocyclic ring include the following.

[Chemical Formula 13]

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹⁰ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹⁰ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹⁰ ) ₄ .

As the ⁺ N (R ¹⁰ ) ₄ , at least two of the four R ^{10 s} are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of four R < ¹⁰ > is preferably 20 to 80, more preferably 20 to 60. [ In the case where ⁺ N (R ¹⁰ ) ₄ exists in the compound (a1), a color filter having less foreign matters can be formed from the colored curable resin composition containing the compound (a1), provided that R ¹⁰ is one of these groups.

Among these, as the substituent is _{^{-R 7, -SO 3 -, -SO}} 3 H, -SO 3 - Z + and ^{_{-SO 2 N (R 8) (}} R 9) are preferred, -R ^7, -SO ₃ ^- the Z ⁺ and ^{_{-SO 2 N (R 8) (}} R 9) is more preferable. In this case, -R ⁷ is more preferably a monovalent alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably a methyl group or an ethyl group. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹⁰ ) ₄ .

-SO ₃ in the formula (a1-1) ^- is a formula ⁽⁵ Z -1) through (Z ⁵ -5) is preferred, preferably in formula (Z ⁵ -1) more selected from the following.

[Chemical Formula 14]

The compound represented by formula (a1-1) is preferably a compound represented by formula (a1-1-1) (hereinafter sometimes referred to as "compound (a1-1-1)"). The compound (a1-1-1) may be a tautomer thereof.

[Chemical Formula 15]

[In the formula (a1-1-1)

R ^1b to R ^4b independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -N R ^11b ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted. R ^1b and R ^2b together may form a ring containing a nitrogen atom, and R ^3b and R ^4b together may form a ring containing a nitrogen atom.

R ^5b and R ^6b independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

The monovalent saturated hydrocarbon groups of 1 to 20 carbon atoms in R ^1b to R ^4b and R ^11b include the same saturated hydrocarbon groups of 1 to 20 carbon atoms in R ¹ to R ⁴ and R ¹⁰ .

The methylene group (-CH ₂ -) included in the saturated hydrocarbon group may be replaced with -O-, -CO-, -N (R ^11b ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, Or -NHCO-. ≪ / RTI > However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.

The saturated hydrocarbon group in R ^1b to R ^4b may have a substituent, and examples of the substituent include an aromatic hydrocarbon group having 6 to 10 carbon atoms and 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 aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group.

Compound (a1-1-1) in R ^1b ~ ^4b R of R ^1b and R ^2b, R ^3b and R ^4b are the same and each a saturated hydrocarbon group, preferably, R ^1b and R ^2b, R ^3b and R ^4b are each straight- More preferably R ^1b and R ^2b , R ^3b and R ^4b are each a linear alkyl group having 1 to 5 carbon atoms, more preferably a combination of R ^1b and R ^2b , R ^3b and R ^4b Are each a combination of two kinds selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a butyl group.

Examples of the ring formed by R ^1b and R ^2b together and the ring formed by R ^3b and R ^4b together include the following.

[Chemical Formula 16]

Examples of the alkyl group having 1 to 6 carbon atoms in R ^5b and R ^6b include those having 1 to 6 carbon atoms in the alkyl groups listed above. Among them, a hydrogen atom is preferable as R ^5b and R ^6b .

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11b include a benzyl group, a phenylethyl group, and a phenylbutyl group.

The compound represented by the formula (a1-1) is preferably a compound represented by the following formula (a1-1-2) (hereinafter sometimes referred to as "the compound (a1-1-2)"). The compound (a1-1-2) may be a tautomer thereof.

[Chemical Formula 17]

[In the formula (a1-1-2)

R ^1c and R ^4c independently represent an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.

p and q independently represent an integer of 0 to 5; When p is 2 or more, plural R ^1c may be the same or different, and when q is 2 or more, plural R ^4c may be the same or different.

R ^2c and R ^3c independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is -O-, -CO -, -N (R ^11c ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-. However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.

R ^1c and R ^2c together may form a ring containing a nitrogen atom, and R ^3c and R ^4c together may form a ring including a nitrogen atom.

R ^5c and R ^6c independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ^11c represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms for R ^1c and R ^4c include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms for R ^1c and R ^4c include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group and an isopropylsulfanyl group.

Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ^1c and R ^4c include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

Among them, R ^1c and R ^4c are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group.

p and q are preferably an integer of 0 to 2, and 1 or 2 is preferable.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^2c , R ^3c and R ^11c include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, , A straight chain alkyl group such as a dodecyl group, a hexadecyl group and an icosyl group; Branched chain alkyl groups such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group; An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and tricyclodecyl group. The monovalent saturated hydrocarbon group of R ^2c , R ^3c and R ^11c is more preferably a C 1-15, more preferably a C 1-10, yet more preferably a C 1-6 saturated hydrocarbon group.

The methylene group (-CH ₂ -) included in the saturated hydrocarbon group may be replaced by -O-, -CO-, -N (R ^11c ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- Or -NHCO-. ≪ / RTI > However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.

The saturated hydrocarbon group in R ^2c and R ^3c may have a substituent, and examples of the substituent include a halogen atom or an aromatic hydrocarbon group having 6 to 10 carbon atoms.

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

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, a mesyl group, a propylphenyl group and a butylphenyl group.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^5c and R ^6c include those having 1 to 6 carbon atoms in the alkyl groups listed above. Among them, a hydrogen atom is preferable as R ^5c and R ^6c .

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11c include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Examples of the compound (a1) include compounds represented by the formulas (I-1) to (I-25). In the formulas (I-1) to (I-25), R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, Hexyl group.

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

Among these compounds, the compounds represented by formulas (I-18) to (I-22) are preferable, and the compounds represented by formula (I-18) Compound, more preferably a compound represented by the formula (I-19).

1-1-2. Squarylium compound

The compound (a) of the present invention is preferably a squarylium compound (a2), more preferably a compound represented by the following formula (a2-1).

≪ EMI ID =

[In the formula (a2-1)

R ^a1 ~ R ^a4 are independently represents a hydrogen atom, a halogen atom, a hydroxy group, an aromatic hydrocarbon having from 6 to 20 carbon atoms which may have a substituent group or a saturated hydrocarbon group of 1 to 20 carbon atoms each, R ^a1 and R ^a5, R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 may form a ring with the carbon atoms to which they are bonded, and R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 and R ^a11 , R ^a4 and R < ^a12 > may form a ring together with the nitrogen atom and the carbon atom to which they are bonded.

R ^a5 to R ^a8 independently represent a hydrogen atom, a hydroxy group, a -SH group, a -CF ₃ group or -NHCO-R ^a23 .

R ^a9 to R ^a12 each independently represent an aromatic hydrocarbon group which may have a substituent, a saturated hydrocarbon group which may have a substituent, a saturated hydrocarbon group which may have a substituent, or an unsaturated aliphatic hydrocarbon group which may have a substituent and which has 4 to 20 carbon atoms, The methylene group constituting the hydrocarbon group or the unsaturated aliphatic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ^a24 ) -, a sulfonyl group or a carbonyl group. R ^a9 and R ^a10 , R ^a11 and R ^a12 may form a ring together with the nitrogen atom to which they are bonded.

R ^a23 represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and the methylene group constituting the monovalent saturated hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ^a25 ) -, a sulfonyl group or a carbonyl group have. However, the adjacent methylene group is not simultaneously substituted with the same group, and the terminal methylene group is not substituted.

R ^a24 and R ^a25 independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

In the formula (a2-1), the halogen atom in R ^a1 to R ^a4 includes a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the formula (a2-1), the aromatic hydrocarbon group represented by R ^a1 to R ^a4 preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms.

Examples of the substituent which the aromatic hydrocarbon group represented by R ^a1 to R ^a4 may have include an alkenyl group having 1 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group and a hexenyl group; An alkyloxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group; A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; An alkyl group having 1 to 6 carbon atoms and substituted with a fluorine atom such as a trifluoromethyl group; And the like.

^Examples of the aromatic hydrocarbon group represented by R ^a1 to R ^a4 include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a biphenyl group, a naphthyl group, an anthryl group and a phenanthryl group; Aralkyl groups such as a benzyl group, a phenylethyl group and a phenylbutyl group; An aryloxy group such as a phenoxy group; And the like.

The saturated hydrocarbon group having 1 to 20 carbon atoms in R ^a1 to R ^a4 and R ^a23 to R ^a25 preferably has 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 8 carbon atoms, And has 1 to 7 carbon atoms. A straight chain alkyl group having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and eicosyl group; Branched chain alkyl groups having 3 to 20 carbon atoms such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, 1-ethylpentyl and 2-ethylhexyl; And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^a23 may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; Cyano; A nitro group; Carbamoyl group; A sulfamoyl group; A hydroxy group; Amino group and the like.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is substituted with an oxygen atom include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- And the like; And the like.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is substituted with an oxygen atom and a carbonyl group include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group; An alkylcarbonyloxy group such as an acetoxy group; An arylcarbonyloxy group such as a benzoyloxy group; And the like.

Further, the groups in which the methylene group constituting the monovalent saturated hydrocarbon group is substituted with -N (R ^a24 ) - or -N (R ^a25 ) - and carbonyl group include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-isopropylcarbamoyl, N-isopropylcarbamoyl, N-isobutylcarbamoyl, N-sec-butylcarbamoyl, N-tert-butylcarbamoyl, , N-1 substituted carbamoyl groups such as N- (1-ethylpropyl) carbamoyl group and N- (1,1-dimethylpropyl) carbamoyl group;

An N, N-diethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-dimethylcarbamoyl group, An N, N-heptylmethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-diethylcarbamoyl group, An N, N-2-substituted carbamoyl group such as a bis (2-ethylhexyl) carbamoyl group; And the like.

Examples of the group in which the methylene group constituting the monovalent saturated hydrocarbon group is substituted with a sulfonyl group and -N (R ^a24 ) - or -N (R ^a25 ) - include an N-methylsulfamoyl group, Butylsulfamoyl group, an N-isopropylsulfamoyl group, an N-butylsulfamoyl group, an N-sec-butylsulfamoyl group, an N-tert- An N-1 substituted sulfamoyl group such as a sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group and an N- (1,3-dimethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-2-substituted sulfamoyl groups such as a hexylsulfamoyl group; And the like.

^{Examples of the} group in which the methylene group constituting the monovalent saturated hydrocarbon group is substituted with -N (R ^a24 ) - or -N (R ^a25 ) - include N-methylamino group, N-ethylamino group, N-propylamino group, (1-ethylpropyl) amino group, N- (1,1-dimethylpropyl) amino group, N-butylamino group, N-isobutylamino group, N-sec- An N-alkylamino group such as an amino group, N- (1,2-dimethylpropyl) amino group, N- (1,2-dimethylhexyl) amino group and N- (1,1,2,2-tetramethylbutyl) amino group;

N, N-diethylamino group, N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-dialkylamino groups such as N, N-butylethylamino group, N, N-bis (1-methylpropyl) amino group, N, N-heptylmethylamino group, ;

N-tert-butylaminomethyl group, N-tert-butylaminomethyl group, N-tert-butylaminomethyl group, N-isopropylaminomethyl group, N-alkylaminomethyl groups such as a butylaminomethyl group, an N-pentylaminomethyl group, an N- (1-ethylpropyl) aminomethyl group and an N- (1,1-dimethylpropyl) aminomethyl group;

An N, N-dimethylaminomethyl group, an N, N-ethylmethylaminomethyl group, an N, N-diethylaminomethyl group, (1-methylethyl) aminomethyl group, N, N-heptylmethylaminomethyl group, N, N-bis (2-ethylhexyl) amino N, N-dialkylaminomethyl groups such as methyl group; And the like.

The ring formed by R ^a1 and R ^a5 , R ^a2 and R ^a6 , R ^a3 and R ^a7 , R ^a4 and R ^a8 together with the carbon atom to which they are bonded is a structure represented by the following formula. In the formula, R ^A1 represents the same group as R ^a1 to R ^a4 , R ^A2 represents the same group as R ^a5 to R ^a8, and R ^A3 represents the same group as R ^a9 to R ^a12 . * Indicates the binding position.

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The ring formed by R ^a1 and R ^a9 , R ^a2 and R ^a10 , R ^a3 , R ^a11 , R ^a4 and R ^a12 together with the nitrogen atom and the carbon atom to which they are bonded is a structure represented by the following formula . In the formula, R ^A1 represents the same group as R ^a1 to R ^a4 , R ^A2 represents the same group as R ^a5 to R ^a8, and R ^A3 represents the same group as R ^a9 to R ^a12 . * Indicates the binding position.

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The aromatic hydrocarbon group which may have a substituent in R ^a9 to R ^a12 preferably has 6 or more carbon atoms, more preferably has 8 or more carbon atoms, preferably has 18 or less carbon atoms, and preferably has 15 or less carbon atoms. ^Examples of the aromatic hydrocarbon group represented by R ^a9 to R ^a12 include an aryl group having 6 to 12 carbon atoms such as a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group; An aralkyl group having 7 to 12 carbon atoms such as a benzyl group, a phenylethyl group and a phenylbutyl group. The aryl group is particularly preferably a phenyl group, and the aralkyl group is particularly preferably a benzyl group.

The aromatic hydrocarbon group represented by R ^a9 to R ^a12 may have a substituent, and examples of the substituent include an alkenyl group having 1 to 5 carbon atoms such as a vinyl group.

The aryl group preferably has a substituent at the o-position of the bonding position, and the aralkyl group preferably has a substituent at the o-position of the alkylene group. ^Examples of the aromatic hydrocarbon group which may have a substituent represented by R ^a9 to R ^a12 include groups represented by the following formulas. In the formula, * represents a bonding position.

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Examples of the saturated hydrocarbon group having 4 to 20 carbon atoms in R ^a9 to R ^a12 include ^{straight chain} hydrocarbon groups such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a hexadecyl group and an eicosyl group A chain alkyl group; And a branched chain alkyl group such as a 2-ethylhexyl group. Examples of the monovalent unsaturated aliphatic hydrocarbon group having 4 to 20 carbon atoms in R ^a9 to R ^a12 include a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group and a dodecenyl group , Straight-chain alkenyl groups such as a hexadecenyl group and an icosenyl group; And the like.

The saturated hydrocarbon group having 4 to 20 carbon atoms in R ^a9 to R ^a12 may have a substituent, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom and a bromine atom; Cyano; A nitro group; Carbamoyl group; A sulfamoyl group; A hydroxy group; Amino group and the like.

^Examples of the ring formed by R ^a9 and R ^{a10 together} with R ^a11 and R ^a12 together with the nitrogen atom to which they are bonded include a structure represented by the following formula.

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Examples of the aralkyl group having 7 to 10 carbon atoms in R ^a24 and R ^a25 include a benzyl group, a phenylethyl group and a phenylbutyl group.

Among them, a hydrogen atom is preferable as R ^a1 to R ^a4 in the formula (a2-1).

R ^a5 to R ^a8 are preferably a hydrogen atom, a hydroxy group or -NHCO-R ^a23 , more preferably a hydrogen atom or a hydroxyl group, still more preferably a hydrogen atom.

R ^a9 to R ^a12 are each preferably an aromatic hydrocarbon group having 8 to 20 carbon atoms which may have a substituent or a saturated hydrocarbon group having 4 to 20 carbon atoms and may have a substituent, more preferably an aromatic hydrocarbon group having 4 to 20 carbon atoms, Is a monovalent aromatic hydrocarbon group having 1 to 20 carbon atoms.

R ^a23 is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably a saturated hydrocarbon group having 1 to 4 carbon atoms.

R ^a24 and R ^a25 each independently represent a saturated hydrocarbon group having 1 to 20 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 4 carbon atoms.

Examples of the groups represented by the following formulas (x-1) and (x-2) include groups represented by formulas (A1-1) to (A1-8).

In these formulas, * indicates the position to which it is bonded, and > N- * can be & gt ^; N ⁺ = *.

[Chemical Formula 29]

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Examples of the group represented by the formulas (x-1) and (x-2) include groups represented by the formulas (A2-1) to (A2- -7). ≪ / RTI > * Denotes the binding position, and > N- * can be & gt ^; N ⁺ = *.

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Specific examples of the compounds represented by the formula (a2-1) in Tables 1 to 4 include the compounds (AI-1) to (AI-97) based on the following formula (AI-a) .

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In formula (AI-a) and in Tables 1 to 4 R ^a1 ~ R ^a8 are the same meaning as R ^a1 R ^a8 ~ in the formula (a2-1), respectively, X ^a1, X ^a2, respectively formula (x -1), and (x-2).

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In addition, (A1-1) to (A1-8), (A2-1) to (A2-7) in Tables 1 to 4 indicate the formulas (A1-1) to (A1-8) ) To the formula (A2-7). Of the formulas (x-1) and (x-2), * indicates the position to which the compound is bonded, and > N- * can be & gt ^; N ⁺ = *. Further, in Tables 1 to 4, NHCO-EHC

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Lt; / RTI > * Indicates the position to join.

The compound (AI-16), the compound (AI-16), the compound (AI-17) and the compound (AI-22) are more preferable from the viewpoint of raw material availability.

1-2. Anion (b)

The anion (b) is an anion having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements.

As the anion, an anionic compound of heteropoly acid or isopoly acid containing tungsten as an essential element is preferable, and anions of tungstic acid, tungstic acid and tungsten-based isopoly acid are more preferable.

Examples of anions of heteropoly acids or isopoly acids containing tungsten as essential elements include tungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , which is a keel type, tungstate ion α- [P ₂ W ₁₈ O ^{_{62] 6-, β- [P 2}} W 18 O 62] 6-, Kane ginhyeong silicon tungstate ion ^{_{α- [SiW 12 O 40] 4-}} , β- [SiW 12 O 40] 4-, γ- [SiW ₁₂ O ₄₀ ] ^4- , further examples include [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ^{_{30 O 110] 14-, α- [}} SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39] 8-, β- [SiW 11 O 39] 8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- , and the like. Among them, the cake ginhyeong of tungstate ion α- [PW ₁₂ O _40] ^3- is particularly preferable.

1-3. The cation (c)

The cation (c) is a cation containing an alkaline earth metal and is preferably at least one member selected from the group consisting of a magnesium cation, a calcium cation, a strontium cation and a barium cation, more preferably a calcium cation or a barium cation. These may be derived from a halogenated alkaline earth metal capable of forming a target and then precipitating, and the halogenated alkaline earth metal may be magnesium chloride, calcium chloride, strontium chloride, barium chloride, and the like.

The compounds of the invention A [Compound ^{(a)] a + b- ·} B [ anions ^{(b)] c - · C} [ cation (c)] ^{d +} if a, = the balance of charges is Aa ⁽⁺⁾ Bc ^{( -)} and Ab ^(-) = Cd ⁽⁺⁾ , and it is also preferable that the relationship of Bc ^(-) = Cd ⁽⁺⁾ is further satisfied. ^{Aa (+), Bc (-} ), Ab (-), the total number of charges of the Cd ⁽⁺⁾ are each an even multiple of that ^{preferably, Aa (+), Bc (} -), Ab (-), Cd (+ ⁾ the total number of charge is more preferably in the preferred, 6, 8 or 12, respectively, than that the 6, 8, 12, 16, 18, 24 or 36.

A is preferably an even number, more preferably 6, 8, 12, 16, 18, 24 or 36, and even more preferably 6, 8 or 12.

a represents a monovalent positive charge, and b represents a monovalent negative charge.

B is preferably an even multiple, more preferably 2 or 4, and even more preferably 2.

c is preferably 3, 4 or 6.

C is preferably 3, 4 or 6.

d is preferably an even multiple, and more preferably two.

1-4. Examples of compounds containing xanthene compounds

Hereinafter, the compound (a) includes the xanthene compound, the anion (b), and the cation (c).

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(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

1-5. Examples of compounds containing squarylium compounds

Hereinafter, the compound (a) includes the squarylium compound, the anion (b), and the compound containing the cation (c).

Hereinafter, Ra represents the following groups.

[Chemical Formula 45]

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(48)

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(50)

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(52)

(53)

The compounds of the present invention can be obtained by reacting a compound represented by the formula (Xa-1a) to a compound represented by the formula (Xa-1h), a compound represented by the formula (Xa-2a) (SQ-1a) to (SQ-1h), the formula (SQ-2a), (SQ-2h), SQ-3a to SQ-3h and SQ-4a to SQ-4h, 5a) to (Xa-5h), more preferably the formula (Xa-5a).

The compound of the present invention can be used as a coloring agent.

2. Coloring curable resin composition

The present invention includes a colored curable resin composition comprising a compound of the present invention (hereinafter sometimes referred to as a colorant (A1)), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

The colorant (A1) may be used in combination of two or more.

The content of the colorant (A1) in the colorant is usually 1 to 100% by mass, preferably 3 to 100% by mass, more preferably 3 to 70% by mass, and still more preferably 3 to 60% by mass.

In addition to the colorant (A1), a dye or pigment as the colorant (A2).

The dyes of the colorant (A2) may be selected from the group consisting of Solvent, Acid, Basic, Reactive, Direct, Disperse or Vat, and known dyes described in Dyeing Note (Color Dyeing). According to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes can be mentioned. Two or more of these dyes may be used in combination.

Specifically, dyes having the following color index (C.I.) numbers can be mentioned. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 112, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Reactive Yellow 2, 76, 116;

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 108, 109, 129, 132, 136, 138, 141;

C.I. Disperse Yellow 51, 54, 76;

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Reactive Orange 16;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid Violet 34, 102;

C.I. Disperse Violet 26, 27;

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

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

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

C.I. Direct Blue 40;

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

C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33;

C.I. Acid Green 3, 5, 9, 25, 27, 28, 41;

C.I. Basic Green 1;

C.I. Bat Green 1 and the like.

The pigment of the colorant (A2) is not particularly limited and a known pigment may be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists) can be mentioned, and two or more pigments can be combined.

Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 194 and 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments such as Pigment Green 7, 36, and 58.

If necessary, the pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group has been introduced, a graft treatment on the surface of the pigment with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method, A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like. The particle size of the pigment is preferably substantially uniform. The pigment can be made into a pigment dispersion in a uniformly dispersed state in a pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. Each of the pigments may be dispersed singly, or various dispersions may be mixed and dispersed.

The pigment dispersant may be a surfactant or the like, and may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specific examples thereof include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shinetsu Kagaku Kogyo K.K.), fullerene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (Manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), and Disperbyk (registered trademark) (manufactured by BICKEMISA).

When a pigment dispersant is used, its amount to be used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the pigment. When the amount of the pigment dispersant is within the above range, a more uniformly dispersed pigment dispersion tends to be obtained.

The content of the colorant (A1) in the colored curable resin composition is usually 0.01% by mass or more and 70% by mass or less, preferably 0.1% by mass or more and 60% by mass or less, more preferably 0.2% Or less, and particularly preferably 0.3 mass% or more and 50 mass% or less. When the content of the colorant (A1) is within the above range, desired spectral or color density can be more readily obtained. In the present specification, the "total amount of solid content" refers to the total amount of components excluding the solvent from the colored curable resin composition of the present invention. The total amount of the solid components and the content of each component thereof can be measured by known analytical means such as liquid chromatography, gas chromatography and the like.

The ratio of the amount of the coloring agent (A1) to the amount of the coloring agent (A2) used (colorant (A1) (in terms of solid content) / colorant (A2) (in terms of solid content) More preferably from 0.5 to 50, even more preferably from 1 to 25, particularly preferably from 1 to 10, and most preferably from 2 to 6. [

≪ Resin (B) >

The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin, and the resin having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride Polymers are more preferred. Examples of such a resin include the following resins [K1] to [K6].

(A) (hereinafter may be referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4, And a monomer (b) having an ethylenically unsaturated bond (hereinafter may be referred to as "(b)")

Resin [K2]: Monomer (c) copolymerizable with (a), (b) and (a) (but different from (a) and (b)) (hereinafter referred to as " ) ≪ / RTI >

Resin [K3]: a copolymer of (a) and (c)

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

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

Resin [K6]: A resin obtained by reacting (a) a copolymer of (b) and (c) with a carboxylic acid anhydride.

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

Unsaturated dicarboxylic acids such as maleic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- A non-cyclic unsaturated compound containing a carboxy group such as;

Unsaturated dicarboxylic acid anhydrides such as maleic anhydride;

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 viewpoints of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

(b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxirane rings, oxetane rings, and tetrahydrofuran rings) and an ethylenic unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group. In the present specification, the term "(meth) acrylic acid" refers to at least one kind selected from the group consisting of acrylic acid and methacrylic acid, and the expressions of "(meth) acryloyl" .

(b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as "(b2)") having an oxiranyl group and an ethylenically unsaturated bond as the monomer (b) (B3) (hereinafter may be referred to as "b3") having a tetrahydrofuryl group and an ethylenically unsaturated bond.

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

The monomer (b1-1) is preferably a monomer having a glycidyl group and an ethylenic unsaturated bond. (meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinyl Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl-o-vinyl benzyl glycidyl ether,? -Methyl- (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyl (Glycidyloxymethyl) styrene, 2,3, 5-tris (glycidyloxymethyl) styrene, , 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000 manufactured by Daicel Co.), 3,4-epoxycyclohexyl (Meth) acrylate (for example, Cyclomer (registered trademark) A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) Die cell production), a compound represented by the formula (1) and a compound represented by the formula (2).

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[In the formulas (1) and (2), R ^a and R ^b independently 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 independently represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

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

* Represents the bonding position with O.]

Examples of the compound represented by the formula (1) include compounds represented by the formulas (1-1) to (1-15) The compounds represented by formulas (1-1), (1-7), (1-9) and (1-11) -7), the compound represented by the formula (1-9) and the compound represented by the formula (1-15) are more preferable.

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(56)

(57)

(58)

[Chemical Formula 59]

(60)

(61)

(62)

Examples of the compound represented by formula (2) include compounds represented by formulas (2-1) to (2-15), and among them, compounds represented by formulas (2-1), (2-3) (2-1), (2-5), (2-7), (2-9) and -7), (2-9) and (2-15) are more preferable.

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≪ EMI ID =

(65)

(66)

(67)

(68)

(69)

(70)

The compound represented by formula (1) and the compound represented by formula (2) may be used alone, or the compound represented by formula (1) and the compound represented by formula (2) may be used in combination. When these are used in combination, the ratio of the compound represented by the formula (1) and the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2) : 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.

(b3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

(B1) is preferably (b1) and (b1) is preferably (b1-2) because the storage stability of the color-curable resin composition is excellent since the reliability of the obtained color filter can be further improved, ).

(meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as "dicyclopentanyl (meth) acrylate" (Meth) acrylate (referred to in the art as "dicyclopentenyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decen-8- Quot; acrylate "), dicyclopentanyloxyethyl (meth) acrylate, (Meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, benzyl (meth) acrylate, (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- Cyclounsaturated compounds;

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

Vinyl group-containing aromatic compounds such as styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; Vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl group-containing amides such as acrylamide and methacrylamide; Esters such as vinyl acetate; Dienes of 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; And the like.

Of these, vinyl group-containing aromatic compounds, dicarbonylimide compounds and bicyclic unsaturated compounds are preferable from the viewpoint of copolymerization reactivity and heat resistance. Specific examples thereof include styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N- Benzyl maleimide and bicyclo [2.2.1] hept-2-ene are preferred.

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene 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).

As the resin (B), 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) ) 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 (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / ( A resin [K2] such as a methacrylic acid / vinyltoluene copolymer, and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; A resin such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) ]; 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; (K6) such as a resin obtained by reacting a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid in addition to tetrahydrophthalic anhydride .

The weight average molecular weight of the resin (B) in terms of polystyrene is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, still more preferably from 5,000 to 30,000, particularly preferably from 6,000 to 25,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution 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, more preferably 1.2 to 4, still more preferably 1.3 to 3, still more preferably 1.5 ~ 2.5.

The acid value (in terms of solid content) of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 170 mg-KOH / g, To 170 mg-KOH / g, more preferably 150 mg-KOH / g or less, and even more preferably 135 mg-KOH / g or less.

The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, and particularly preferably 13 to 60% by mass, based on the total amount of the solid components, Mass%. When the content of the resin (B) is in the above range, the coloring pattern is easily formed, and the resolution and residual film ratio of the coloring pattern tends to be improved.

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and a (meth) acrylic acid ester structure Are preferred. The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds, more preferably a polymerizable compound having five to six ethylenic unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and (a), (b) and (c) described above. Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Methacrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (Meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, (Meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hex (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

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

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

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually from 5 to 65% by mass, preferably from 7 to 65% by mass, more preferably from 10 to 60% by mass, Preferably from 13 to 60% by mass, and particularly preferably from 17 to 55% by mass. The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65 to 80:20, to be. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a coloring 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 initiating polymerization by generating an active radical or acid by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and nonimidazole compounds.

Examples of the O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- -Acetoxy-l- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl Benzoyl} -9H-carbazol-3-yl] ethan-1-imine, N- acetoxy- 1- [9- ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-imine and N-benzoyloxy- ] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE 01, OXE 02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1- (4-phenylsulfanylphenyl) Imine and at least one member selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

The alkylphenone compound is preferably a 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- -1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. IRGACURE 369, 907 and 379 (all manufactured by BASF) can be used.

The alkylphenone compound is preferably a 2-hydroxy-2-methyl-1-phenylpropan-1-one or a 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one,?,? - diethoxyacetophenone and benzyldimethylketone You can ride.

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

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

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373 etc.), 2,2'- Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxy) Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) ) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403 and Japanese Patent Application Laid-open No. 62-174204) Imidazole compounds in which the phenyl group at the 4 ', 5,5'-position is substituted by a carboalkoxy group (see, for example, JP-A-07-010913). Among them, a compound represented by the following formula and a mixture thereof are preferable.

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Other polymerization initiators 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 a polymerization initiator (particularly an amine polymerization initiator) which will be described later.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 1 to 30 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Particularly preferably 1 to 20 parts by mass.

<Polymerization Initiator>

The polymerization initiation aid is a compound or sensitizer used for promoting the polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiator, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator include an amine-based polymerization initiator, an alkoxyanthracene-based polymerization initiator, a thioxanone-based polymerization initiator, and a carboxylic acid-based polymerization initiator.

Examples of the amine-based polymerization initiator include alkanolamines such as triethanolamine, methyldiethanolamine and triisopropanolamine; Aminobenzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4'- Amino) benzophenone, among which alkylaminobenzophenones such as 4,4'-bis (diethylamino) benzophenone are preferred. Among them, alkylaminobenzophenone is preferable, and 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-based polymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone polymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1-chloro- &Lt; / RTI &gt;

Examples of the carboxylic acid-based polymerization initiator include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid , Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

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

&Lt; Solvent (E) >

The solvent (E) is not limited, and solvents commonly used in the field may be used alone or in combination of two or more. Specifically, an ester solvent (a solvent containing -COO- and no -O- in the molecule), an ether solvent (a solvent containing -O- and -COO- in the molecule), an ether ester solvent (Including a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- and no -COO- in the molecule), an alcohol solvent (including OH in the molecule and -O-, And -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

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

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

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 acetate , There may be mentioned di-ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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

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

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

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

These solvents may be used in combination of two or more.

Among these solvents, an organic solvent having a boiling point of 120 ° C or more and 210 ° C or less at 1 atm is preferable from the viewpoint of coatability and dryness. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone are preferable, Propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate , N, N-dimethylformamide and N-methylpyrrolidone are more preferred.

The content of the solvent (E) is usually from 70 to 95 mass%, preferably from 75 to 92 mass%, more preferably from 75 to 90 mass%, based on the total amount of the colored curable resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density tends not to be insufficient when the color filter is formed, so that display characteristics tend to be good.

<Leveling agent>

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

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (Manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Shin-Etsu Chemical Co., Ltd.), KP321, KP323, KP324, KP326, KP340 and KP341 (Manufactured by Momentive Performance Materials Japan Joint Corporation).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is preferable to use a mixture of FLORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper (equivalent) F171, copper (same) F-177, F183, F554, R30, RS-718-K (manufactured by DIC), F-TOP (registered trademark) EF301, (Trade name) EF303, EF351 and EF352 (manufactured by Mitsubishi Material Denshi Kasei Co., Ltd.), SURFLON (registered trademark) S381, S382, SOT101, ) SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Co., Ltd.).

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

The content of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, more preferably 0.001 mass% or more and 0.2 mass% or less, relative to the total amount of the colored curable resin composition. Preferably 0.002 mass% or more and 0.1 mass% or less, and particularly preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

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, as required.

&Lt; Process for producing colored curable resin composition >

The colored curable resin composition of the present invention can be obtained, for example, by mixing a compound (colorant (A1)), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) Auxiliaries, and other ingredients. In addition to the colorant (A1), a colorant (A2) such as a pigment or a dye may be further mixed. It is preferable to use the pigment in a state of a pigment dispersion in which the pigment is mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended.

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

<Manufacturing Method of Color Filter>

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, and then the colored composition layer is formed by drying to expose and develop the colored composition layer through a photomask. A colored coating film which is a cured product of the colored composition layer can be formed by photolithography without using and / or developing a photomask during exposure. The coloring pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the color filter to be produced can be suitably adjusted according to the purpose or use, and is usually 0.1 to 30 탆, preferably 0.1 to 20 탆, more preferably 0.5 to 6 탆.

As the substrate, a glass plate, a resin plate, silicon, and aluminum, silver, silver / copper / palladium alloy thin film and the like are formed on the substrate. On this substrate, a separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The formation of each color pixel by the photolithographic method can be performed by a known or common apparatus or condition. For example, it can be manufactured as follows.

First, the colored curable resin composition is coated on a substrate, and then heated and dried (pre-baked) and / or reduced-pressure dried to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer. Examples of the application method include a spin coating method, a slit coating method, and a slit and spin coating method.

The coloring composition layer is then exposed through a photomask for forming a desired coloring pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire surface of the exposure surface with a parallel light beam or accurately align the photomask with the substrate on which the coloring composition layer is formed. A coloring pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developer, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The developing method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle at the time of development. It is preferable to rinse after development.

It is preferable to perform post-baking further on the obtained coloring pattern. The color filter having the coloring pattern or the colored coating film thus obtained may be further provided with a surface coating treatment for imparting various properties.

The color filter formed from the colored curable resin composition of the present invention 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 present invention will be described in more detail with reference to examples. In the examples, "%" and "parts" indicating the content or amount are based on mass unless otherwise specified.

Example  One.

To 5.0 parts of the compound represented by the formula (1-1), 400 parts of methanol was added and the mixture was stirred at 20 ° C to 30 ° C for 1 hour to obtain a solution. 400 parts of ion-exchanged water was added to this solution and stirred for 2 hours to obtain a solution (1-1A). On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of Phosphorus 12 tungstate hydrogencarbonate, and the mixture was stirred at 20 ° C to 30 ° C for 1 hour. Then, 28.8 parts of methanol was added and stirred for 2 hours to obtain solution (1-1B). To the solution (1-1A) was added the solution (1-1B) and barium chloride (1.0 part) and the mixture was stirred at 20 ° C to 30 ° C for 24 hours. The resulting precipitate was filtered off by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The obtained crystals were dried at 60 DEG C for 24 hours to obtain 6.3 parts of a compound represented by the formula (1-1P) (the compound represented by the formula (1-1P) was the same as the compound represented by the formula (Xa-5a) It means.

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(73)

Synthesis of resin

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was poured into a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 DEG C with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane- A solution prepared by dissolving 171 parts of a mixture of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate (trade name: "E-DCPA &quot;, manufactured by Daicel Chemical Industries, Ltd.) Was added dropwise over about 5 hours. On the other hand, a solution prepared by dissolving 26 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was charged into a flask And added. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of the copolymer and resin (B-1) having a solid content of 43.5%. The obtained resin (B-1) had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

&Lt; EMI ID =

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

Device; HLC-8120 GPC (manufactured by Tosoh Corporation)

column; TSK-GEL G2000 HXL

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01 mass%

Dose; 50 μL

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 in the above was regarded as molecular weight distribution.

Preparation of colored curable resin composition

Example 2.

Compound (A1): 0.8 part of a compound represented by the formula (1-1P);

Alkali-soluble resin (B): 50 parts of resin (B-1) (in terms of solid content);

Polymerizable compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.);

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

Solvent (E): 700 parts of 1-methyl-2-pyrrolidone; And

Leveling agent (F): 0.1 part of Megapack (registered trademark) F554 (DIC) was mixed to obtain a colored curable resin composition.

Comparative Example 1

Dye (A1): 0.6 part of the compound represented by the formula (1-1);

Alkali-soluble resin (B): 50 parts of resin (B-1) (in terms of solid content);

Polymerizable compound (C): 50 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.);

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

Solvent (E): 700 parts of propylene glycol monomethyl ether acetate; And

Leveling agent (F): 0.1 part of Megapack (registered trademark) F554 (DIC) was mixed to obtain a colored curable resin composition.

Formation of patterns

The colored curable resin composition was coated on a 2 inch square glass substrate (Eagle XG; Corning) by spin coating, and then pre-baked at 100 ° C for 3 minutes to obtain a composition layer. After cooling, an exposure amount (based on 365 nm) of 150 mJ / cm ² was measured using an exposure machine (TME-150 RSK, manufactured by Topcon Co., Ltd.) at an interval of 100 m between the glass substrate on which the composition layer was formed and the quartz glass photomask Light irradiation. As the photomask, a 100 μm line and space pattern is used. After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, washed with water and then postbaked at 220 DEG C for 20 minutes in an oven To obtain a pattern.

Heat resistance evaluation

The coating film of the colored curable resin composition was heated at 230 占 폚 for 20 minutes and the color difference? Eab * before and after the coating film heating was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of evaluating the heat resistance of the coating film obtained in Example 2, the color difference (? Eab *) was 4.3. As a result of evaluating the heat resistance in the same manner as in Comparative Example 1, the color difference (ΔEab *) was 12.9, indicating that the present compound was excellent in heat resistance.

When a colored curable resin composition containing the present compound is used, a coating film having good heat resistance can be provided. The coating film 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.

Claims (7)

(A) having a cation and an anion in a molecule,
(B) having at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, and
And a cation (c) containing an alkaline earth metal. The compound according to claim 1, wherein the compound (a) is a xanthene compound (a1). The compound according to claim 2, wherein the xanthene compound (a1) is a compound represented by the formula (a1-1).
[Chemical Formula 1]

[In formula (a1-1), R ¹ to R ⁴ independently represent a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -N (R ¹⁰ ) -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- Or -NHCO-. &Lt; / RTI &gt; However, adjacent -CH ₂ - is not substituted at the same time with the same group, and -CH ₂ - at the terminal is not substituted.
R ¹ and R ² may together form a ring containing a nitrogen atom, and R ³ and R ⁴ together may form a ring containing a nitrogen atom.
R ⁵ and R ⁶ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ¹⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. The method according to claim 1,
Wherein the cation (c) is at least one member selected from the group consisting of a magnesium cation, a calcium cation, a strontium cation and a barium cation. A colored curable resin composition comprising a compound, a resin, a polymerizable compound and a polymerization initiator according to any one of claims 1 to 4. A color filter formed from the colored curable resin composition according to claim 5. A liquid crystal display device having the color filter according to claim 6.