KR102344036B1 - Colored curable resin composition, color filter and display device - Google Patents

Abstract

[Problem] The chemical resistance of the color filter formed from the conventional colored curable resin composition may not be fully satisfactory.
[Solution Means] The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) comprises a xanthene skeleton and - A compound containing an anion having an SO ₃ ^— group and/or a —COO ^— group and a metal cation having a divalent or higher value is contained.
In addition, the present invention relates to a color filter which is a coating cured product of the colored curable resin composition, and a display device including the same.

Description

Colored curable resin composition, a color filter, and a display device TECHNICAL FIELD

The present invention relates to a colored curable resin composition.

Colored curable resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display device, an electroluminescent display device, and a plasma display. As such a colored curable resin composition, the colored curable resin composition containing the compound etc. which are represented by a following formula are known (patent document 1).

[Formula 1]

[Patent Document 1] Japanese Patent Laid-Open No. 2010-32999

The chemical-resistance of the color filter formed from the colored curable resin composition containing the conventionally known said compound may not be fully satisfactory.

The present invention includes the following inventions.

[1] A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D) are included,

The colorant (A) is, xanthene skeleton and -SO ₃ ^- groups and / or -COO ^- anion having a group and a colored curable resin composition containing a compound including a divalent or more metal cations.

[2] The colored curable resin composition according to [1], wherein the compound is a compound represented by formula (Ia-2).

[Formula 2]

[In formula (Ia-2), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group of ^{R 31} and R ^{32 is,} -SO ₃ ^- , -COO ^- , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom may be substituted, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is -SO ₃ ^- , -COO ^- or C 1 It may be substituted with the alkoxy group of ~3, and _{-CH 2} - contained in the monovalent saturated hydrocarbon group of ^{R 31} and R ³² may be substituted with -O-, -CO- or -NR ^{11 -.}

R ³³ and R ³⁴ each independently represent -SO ₃ ^- , -COO ^- , 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.

R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p1 and p2 each independently represent the integer of 0-5. When p1 is 2 or more, some R ³³ may be same or different, and when p2 is 2 or more, some R ³⁴ may be same or different.

R ¹¹ 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.

Mr ⁺ represents an r-valent metal cation.

k represents the integer of 1-3. q represents an integer greater than or equal to 1; R represents an integer of 2 or more. n represents an integer greater than or equal to 1; However, k, q, n, and r satisfy k×q=n×r.]

[3] The colored curable resin composition as described in [1] or [2] which does not contain a dispersing agent different from 　 resin (B).

[4] A color filter which is a coating cured product of the colored curable resin composition according to any one of [1] to [3].

[5] A display device comprising the color filter according to [4].

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the color filter excellent in chemical-resistance can be formed.

The colored curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator, The said coloring agent (A) is a xanthene skeleton, -SO ₃ ^- group, and/or -COO ^- it contains a compound (I) containing the anion and a divalent or more metal cations having a group. It is preferable that the colored curable resin composition of this invention does not contain the dispersing agent different from resin (B). The colored curable resin composition of this invention may contain the solvent (E) and the leveling agent (F). Further, the compound (I) includes its tautomers, stereoisomers and salts thereof. In addition, each component and functional group illustrated below can be used individually or in combination, respectively.

In the compound (I), -SO ₃ ^- groups and / or -COO ^- total number of the groups are preferably 2-4 individual, and more preferably two or three individuals.

In the said compound (I), it is preferable that it is 1-4, and, as for the number of _{objects of -SO 3} ^{- group, it is more preferable that it is 1-3.}

In the compound (I), -COO ^- total number of the groups, 1 to 3 it is preferable, and more preferably one or two.

In the compound (I), the -SO ₃ ^- group and/or the -COO ^- group may be directly bonded to the xanthene skeleton, or to the xanthene skeleton via at least one group selected from ^{-R 50} - and -NR ^{51 -} You may combine them. -R ⁵⁰ - is preferably bonded to the 9th-position of the xanthene skeleton, and -NR ⁵¹ - is preferably bonded to the 3rd and/or 6th-position of the xanthene skeleton.

R ⁵⁰ represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R ⁵¹ represents a hydrogen atom, a divalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent.

Examples of the divalent or higher metal cation include alkaline earth metal ions such as magnesium ions, calcium ions, strontium ions, and barium ions; titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, copper ions, etc. transition metal ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and bismuth ions are exemplified, alkaline earth metal ions and transition metal ions are preferred, calcium ions, magnesium ions An ion, a barium ion, a manganese ion, an iron (III) ion, and a cobalt (II) ion are more preferable.

It is preferable that the valence of a metal cation is 2-5, More preferably, it is 2-4, More preferably, it is 2-3.

The compound (I) is preferably a compound represented by the formula (Ia) (hereinafter, may be referred to as “compound (Ia)”).

[Formula 3]

[In formula (Ia), R ¹ to R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a monovalent aromatic group having 6 to 10 carbon atoms which may have a substituent A hydrocarbon group is represented and -CH ₂ - contained in the monovalent saturated hydrocarbon group may be substituted with -O-, -CO-, or -NR ^{11 -.} At least one stage of R ¹ ~ R ^{4 1-valent} saturated hydrocarbon group, and R ¹ ~ R ^{4 1-valent} aromatic hydrocarbon group represented by the represented by the group, as a substituent -SO ₃ ^- group has ^- groups and / or -COO. R ¹ and R ² may be taken together to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be taken together to form a ring containing a nitrogen atom.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

R ¹¹ 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.

Mr ⁺ represents an r-valent metal cation.

k represents the integer of 1-3. q represents an integer greater than or equal to 1; R represents an integer of 2 or more. n represents an integer greater than or equal to 1; However, k, q, n, and r satisfy k×q=n×r.]

In the following description, the side having a negative charge among compound (Ia) is sometimes referred to as an anion (Ia-A). The said anion (Ia-A) is represented by a formula (Ia-A). The anion (Ia-A) includes its tautomers and stereoisomers.

[Formula 4]

[In formula (Ia-A), R ¹ to R ⁷ , k have the same meaning as above.]

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 mesityl group, a propylphenyl group, and a butylphenyl group. Groups R ¹ ~ R ^{4 1-valent} aromatic hydrocarbon group having 6 to 10 in, preferably a phenyl group. Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ⁵⁰ and R ⁵¹ include groups in which one of the hydrogen atoms contained in the ^{monovalent aromatic hydrocarbon group for R 1} to R ^{4 is a bond.}

Examples of the substituent which the monovalent or divalent aromatic hydrocarbon group for R ¹ to R ⁴ , R ⁵⁰ , and R ⁵¹ _{may have include -SO 3} ^- , -COO ^- , a halogen atom, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- can be exemplified by _{^{Z +, -COOH, -CO 2 R}} 8, -SR 8, -SO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ^10, It is preferable that these substituents have substituted the hydrogen atom contained in the monovalent|monohydric or divalent aromatic hydrocarbon group. Among these, as the _{^{substituent, -SO 3 -, -COO -,}} -SO 3 H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are _{^{preferred, -SO 3 -, -COO -,}} -SO 3 ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ is the more preferred. Examples of _{^{Z +, -SO 3 - - -SO}} 3 In this case, the N (R ¹¹⁾ ₄ are preferred. The R ¹ ~ R ⁴ is these groups, in the colored curable resin composition of the present invention comprising the compound (I), less generation of foreign matter, can also form a color filter having excellent heat resistance.

R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with a halogen atom.

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, —CO It may be substituted with -, -NH- or -NR ^{8 -, and R 9} and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ¹ to R ⁴ and R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and a ox group. linear alkyl groups such as tyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl and 2-ethylhexyl; A C3-C20 alicyclic saturated hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, is mentioned. As for carbon number of the said monovalent saturated hydrocarbon group, it is more preferable that it is 1-10, It is still more preferable that it is 1-6, It is still more preferable that it is 1-4. As the divalent saturated hydrocarbon group having 1 to 20 carbon atoms for ^{R 50} and R ⁵¹ , one hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms ^{for R 1} to R ^{4 is a bond.} can be lifted

The hydrogen atom contained in the monovalent or divalent saturated hydrocarbon group in ^{R 1} to R ⁴ , R ⁵⁰ and R ⁵¹ _{is, for example, —SO 3} ^— , —COO ^— , a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms. It may be substituted with a group or a halogen atom, Preferably it may be substituted with -COO- ^{, a C6-} C10 monovalent|monohydric aromatic hydrocarbon group, or a halogen atom. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted for the hydrogen atom of the monovalent or divalent saturated hydrocarbon group of R ¹ to R ⁴ , R ⁵⁰ and R ⁵¹ include 6 carbon atoms in ^{R 1} to R ^{4 .} The same groups as the groups exemplified as the monovalent aromatic hydrocarbon group of ~10 can be mentioned.

The ^{hydrogen atom contained in the monovalent saturated hydrocarbon group for R 9} and R ¹⁰ may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

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.}

[Formula 5]

-OR ⁸ includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group. An alkyloxy group etc. are mentioned.

As -CO ₂ R ⁸ , for example, alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group, etc. can be heard

-SR ⁸ as, for example, and methyl sulfanyl group, ethyl sulfanyl group, a butyl sulfanyl group, hexyl sulfanyl group, a sulfanyl group, and decyl Ikoma chamber alkyl sulfanyl group such as a sulfanyl group.

Examples of -SO ₂ R ^8, for example, there may be mentioned an alkylsulfonyl group such as a methyl sulfonyl group, ethyl sulfonyl, butyl sulfonyl group, hexyl sulfonyl group, sulfonyl group and decyl Ikoma room sulfonyl group.

As -SO ₃ R ⁸ , for example, an alkyloxysulfonyl group such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and an icosyloxysulfonyl group A phonyl group etc. are mentioned.

-SO ₂ NR ⁹ R ^{10 is} , for example, a sulfamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diyl, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) N-1 substituted sulfamoyl groups such as sulfamoyl group, N-(1,5-dimethylhexyl)sulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group;

N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N such as N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group, An N-2 substituted sulfamoyl group etc. are mentioned.

As a C1-C6 alkyl group in R<^6> and R<^7> , a C1-C6 thing is mentioned among the alkyl groups mentioned above. Especially, as R<^6> , R<^7> , a hydrogen atom is preferable.

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

Z ⁺ is ⁺ N(R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ¹¹ ) ₄ .

The N ⁺ (R ¹¹⁾ Examples _4, preferably four of R ^11, at least two of the monovalent saturated hydrocarbon group having a carbon number of 5-20. Moreover, 20-80 are preferable and, as for total carbon number of four R<^{11>, 20-60 are more preferable.}

k is an integer of 1-3, and it is preferable that it is an integer of 1-2.

q is an integer of 1 or more, it is preferable that it is 1-5, More preferably, it is 1-4, More preferably, it is 1-3.

_{It is preferable that 2-4 pieces of -SO 3} ^- groups are contained in the compound represented by Formula (Ia), and it is also preferable that 1 -SO ₃ ^- group and 1-3 pieces of -COO ^- groups are contained.

In the formula (Ia), -SO ₃ ^- group, at least R ¹ ~ R ⁴ substituted with one 1 to 3 of the hydrogen atoms contained more aromatic hydrocarbon groups represented by valence and it is more preferred that at least R ¹ ~ R ⁴ It is more preferable that one or two of the hydrogen atoms contained in the monovalent aromatic hydrocarbon group represented by are substituted.

In the formula (Ia), -COO ^- group, a hydrogen atom included in the monovalent saturated hydrocarbon groups represented by one, two, or three, or R ¹ ~ R ⁴ of the hydrogen atoms contained groups monovalent aromatic hydrocarbon group represented by R ¹ ~ R ⁴ the more it preferred that substituted 1 to 3, and which comprises groups monovalent saturated hydrocarbon represented by one or two or R ¹ ~ R ⁴ of the hydrogen atoms contained groups monovalent aromatic hydrocarbon group represented by R ¹ ~ R ⁴ It is more preferable that one or two of the hydrogen atoms are substituted.

In the compound represented by formula (Ia), -SO substituting a hydrogen atom contained groups one aromatic hydrocarbon ₃ ^- groups and / or ^-COO-group of the total number of individuals that are one preferred, and one saturated hydrocarbon groups -SO ₃ for replacing the hydrogen atom contained ^- groups and / or -COO ^- total number of the groups is preferably 1 individual.

Examples ^{of the r-valent metal cation represented by Mr +} include alkaline earth metal cations such as magnesium ion, calcium ion, strontium ion, and barium ion; titanium ion, zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper transition metal cations such as ions; and typical metal cations such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and bismuth ions, and alkaline earth metal cations and transition metal cations are preferred, calcium An ion, a magnesium ion, a barium ion, a manganese ion, an iron (III) ion, and a cobalt (II) ion are more preferable.

r is an integer of 2 or more, it is preferable that it is 2-5, More preferably, it is 2-4, More preferably, it is 2-3.

n is an integer of 1 or more, it is preferable that it is 1-3, More preferably, it is 1-2.

In formula (Ia), k, q, n, and r satisfy kxq=nxr. For this reason, compound (Ia) becomes a valence of 0, ie, an electrically neutral compound.

As a combination of r and k, (I)-(VI) are preferable, and (I)-(IV) are more preferable.

(I) a combination in which r is 2 and k is 1

(II) a combination in which r is 3 and k is 1

(III) a combination in which r is 2 and k is 2

(IV) a combination in which r is 3 and k is 2

(V) a combination in which r is 2 and k is 3

(VI) a combination in which r is 3 and k is 3

In compound (Ia), R ¹ and R ⁴ are each independently preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R ² and R ³ are, independently of each other, a substituent It is preferable that it is a C1-C20 monovalent saturated hydrocarbon group which you may have, and it is preferable that R<^6> and R<^7> are mutually independently a hydrogen atom.

In compound (Ia), R ¹ and R ⁴ are each independently more preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have at least one selected from a saturated hydrocarbon group and a —SO ₃ ^{— group.} and R ² and R ³ are each independently more preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a ^{—COO — group, and R 6} and R ⁷ are each independently a hydrogen atom, more desirable.

Compound (Ia) may combine 2 or more types. When combining two or more types of compound (Ia), a combination of (I) and (III) or a combination of (II) and (IV) is preferable.

As the compound (Ia), a compound represented by the formula (Ia-1) (hereinafter sometimes referred to as “compound (Ia-1)”) is preferable. Compound (Ia-1) may be a tautomer or stereoisomer thereof.

[Formula 6]

[In formula (Ia-1), R ²¹ to R ²⁴ each independently represent a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. R stage at least one of a monovalent aromatic hydrocarbon group represented by the dog ²¹ ~ R ²⁴ 1-valent saturated hydrocarbon group, and R ²¹ ~ R ²⁴ may appear to have, as a substituent -SO ₃ ^- group has ^- groups and / or -COO. R ²¹ and R ²² may be taken together to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be taken together to form a ring containing a nitrogen atom.

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group may be substituted with _{-SO 3} ^- or -COO ^-.

k, q, r, n and Mr ⁺ have the same meaning as above.]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms for R ²¹ to R ²⁴ include the same groups as the monovalent aromatic hydrocarbon group for ^{R 1} to R ^{4 above.} Hydrogen atoms contained groups aromatic hydrocarbon monovalent art _{^{1, -SO 3 -, -COO -,}} -SO 3 H, -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁵ or -SO ₂ NHR ^25.

Z1 ⁺ is ⁺ N(R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N(R ²⁷ ) ₄ .

R ²⁵ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

As a combination of ^{R 21} to R ^{24 , R 21} and R ²³ are hydrogen atoms, R ²² and R ²⁴ are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is —SO _{^{3 -, -COO -, -SO 3}} H, -SO 3 - as Z1 ^+, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ is preferably substituted. A more preferable combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the monovalent aromatic hydrocarbon group are -SO ₃ ^- , - COO ^-, -SO ₃ ^-, which will be substituted with Z1 ⁺ or -SO ₂ NHR ^26.

The ^{ring containing a nitrogen atom formed by R 21} and R ²² together and the ring containing a nitrogen atom formed by R ²³ and R ²⁴ together include the same ring as the ring formed by ^{R 1} and R ^{2 together.} can be heard Especially, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

[Formula 7]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms for R ²⁵ to R ²⁷ include the same groups as the ^{monovalent saturated hydrocarbon group for R 8} to R ^{11 .}

When R ²¹ to R ²⁴ are -R ²⁶ , -R ²⁶ is each independently preferably a methyl group, an ethyl group or a propyl group.

Also, -SO ₃ R ²⁶ and -SO ₂ R ²⁶ as in the NHR ^26, a branched alkyl group having 3 to 20 carbon atoms are preferred, the branched chain alkyl group having a carbon number of 6 to 12 more preferred, and 2-ethylhexyl is more preferable.

The N ⁺ (R ²⁷⁾ Examples _4, preferably four of R ^27, at least two of the monovalent saturated hydrocarbon group having a carbon number of 5-20. Further, the total carbon number of R 4 is ²⁷ 20 to 80 is preferred, more preferably from 20 to 60. ^{When +} N(R ²⁷ ) ₄ exists in compound (Ia-1) ^{, R 27} may be the same or different.

_{It is preferable that 2-4 pieces of -SO 3} ^- groups are contained in the compound represented by Formula (Ia-1), and it is also preferable that one -SO ₃ ^- group and 1-3 pieces of -COO ^- groups are contained.

In the formula (Ia-1), the -SO ₃ ^- group is more preferably substituted for at least 1 to 3 of the hydrogen atoms contained in the monovalent aromatic hydrocarbon group represented by ^{R 21} to R ^{24 , and at least R 21} to It is more preferable that 1-2 of the hydrogen atoms contained in the C6-C10 monovalent|monohydric aromatic hydrocarbon group represented by R<^{24> are substituted.}

In the formula (Ia-1), 1 ~ 3 of -COO ^- group, R ²¹ ~ R ²⁴ include a hydrogen atom that is a monovalent saturated hydrocarbon groups represented by R ²⁶ is a hydrogen atom or a monovalent aromatic hydrocarbon groups containing 1 indicated by 1 It is more preferable to substitute ∼3, and replace ^{1 or 2} of the hydrogen atoms contained in the monovalent aromatic hydrocarbon group represented by ^{R 21} to R ²⁴ or the hydrogen atoms contained in the monovalent saturated hydrocarbon group represented by R 26 , It is more preferable to have

In the compound represented by formula (Ia-1), 1 -SO ₃ for replacing the hydrogen atom contained aromatic hydrocarbon groups ^- groups and / or -COO ^- total number of the group is preferably in one individual, one saturated -SO ₃ for replacing the hydrogen atom contained hydrocarbon groups ^- groups and / or -COO ^- total number of the groups is preferably 1 individual.

In compound (Ia-1), R ²¹ and R ²³ are each independently preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and R ²² and R ²⁴ are each independently It is preferable that it is a C1-C20 monovalent|monohydric saturated hydrocarbon group which may have a substituent, and it is preferable ^{that the r-valent metal cation represented by Mr +} is an alkaline-earth metal cation and a transition metal cation.

In compound (Ia-1), R ²¹ and R ²³ are each independently a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have at least one selected from a saturated hydrocarbon group and a —SO ₃ ^{— group.} More preferably, R ²² and R ²⁴ are each independently a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a ^{-COO -} group, the r-valent metal cation represented by ^{Mr + is a calcium ion;} It is more preferable that they are a magnesium ion, a barium ion, a manganese ion, an iron (III) ion, and a cobalt (II) ion.

Further, as the compound (Ia), a compound represented by the formula (Ia-2) (hereinafter sometimes referred to as “compound (Ia-2)”) is also preferable. Compound (Ia-2) may be a tautomer or stereoisomer thereof.

[Formula 8]

[In formula (Ia-2), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group of ^{R 31} and R ^{32 is,} -SO ₃ ^- , -COO ^- , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom may be substituted, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is -SO ₃ ^- , -COO ^- or C 1 It may be substituted with the alkoxy group of ~3, and _{-CH 2} - contained in the monovalent saturated hydrocarbon group of ^{R 31} and R ³² may be substituted with -O-, -CO- or -NR ^{11 -.}

R ³³ and R ³⁴ each independently represent -SO ₃ ^- , -COO ^- , 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.

R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.

p1 and p2 each independently represent the integer of 0-5. When p1 is 2 or more, some R ³³ may be same or different, and when p2 is 2 or more, some R ³⁴ may be same or different.

R ¹¹ , q, r, n and Mr ⁺ have the same meaning as above.]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms for R ³¹ and R ³² include a group having 1 to 10 carbon atoms among those ^{for R 8 .}

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted for the hydrogen atom contained in the monovalent saturated hydrocarbon group in R ³¹ and R ³² include the same groups as those in ^{R 1 .}

As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, etc. are mentioned, for example.

It is preferable that R ³¹ and R ³² are each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ 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 in R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group and an isopropylsulfonyl group.

As R ³³ and R ³⁴ , -SO ₃ ^- , -COO ^- or an alkyl group having 1 to 4 carbon atoms is preferable, and -SO ₃ ^- , -COO ^- or a methyl group is more preferable.

The integer of 0-2 is preferable and, as for p1 and p2, 1 or 2 is preferable.

Formula (Ia-2) compound, 2 to 4 represented by -SO ₃ ^- group is preferably contained, and the one -SO ₃ ^- it is also desirable that contains groups ^- group 1 to 3 -COO.

In the formula (Ia-2), have one to 3 of R ³³ and R ³⁴ -SO ₃ ^- group, and more preferably, R ³³ and R 1 ~ ³⁴ 2 -SO ₃ dogs of ^- is more preferably caused.

In the formula (Ia-2), 1 to 3 of ^{R 33} and R ^{34 are -COO -} groups, or 1 to 3 hydrogen atoms included in the monovalent saturated hydrocarbon group in which the ^{-COO -} group ^{is represented by R 31} to R ^{32 .} More preferably, one or two of ^{R 33} and R ^{34 are -COO -} groups, or -COO ^- groups are 1 to 2 of the hydrogen atoms contained in the monovalent saturated hydrocarbon group represented by ^{R 31} to R ^{32 .} It is more preferable to substitute .

In the compound represented by formula (Ia-2), 1 -SO ₃ for replacing the hydrogen atom contained aromatic hydrocarbon groups ^- groups and / or -COO ^- total number of the group is preferably in one individual, one saturated -SO ₃ for replacing the hydrogen atom contained hydrocarbon groups ^- groups and / or -COO ^- total number of the groups is preferably 1 individual.

In compound (Ia-2), R ³¹ and R ³² are each independently preferably a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ³³ and R ³⁴ are each independently -SO ₃ ^- , -COO ^- is preferable, ^{the r-valent metal cation represented by Mr +} is preferably an alkaline earth metal cation or a transition metal cation, and p1 and p2 are, independently of each other, an integer of 0 to 4 it is preferable

In compound (Ia-2), R ³¹ and R ³² are each independently more preferably a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms which may have a ^{-COO - group, R 33} and R ³⁴ are each other Independently, it is more preferably _{-SO 3} ^{- , and the r-valent metal cation represented by Mr +} is more preferably a calcium ion, a magnesium ion, a barium ion, a manganese ion, an iron (III) ion, or a cobalt (II) ion. and p1 and p2 are each independently more preferably 0 or 1.

Examples of the anion (Ia-A) include an anion represented by formulas (Aa-1) to (Aa-88).

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

As compound (I), the following compounds are preferable.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

Among them, compounds (I-1) to (I-12), (I-89) to (I-100), (I-177) to (I-188), (I-265) to (I-276) ), (I-353) to (I-364) are preferable, and compounds (I-7), (I-8), (I-95), (I-96), (I-183), (I -184), (I-271), (I-272), (I-359), (I-360), (I-388), and (I-427) are more preferable.

In the colored curable resin composition of the present invention, the content of the compound (I) is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, with respect to the total amount of solid content of the colored curable resin composition, More preferably, it is 0.5-5 mass %.

The "total amount of solid content" in this specification means the quantity which removed content of the solvent from the total amount of colored curable resin composition. The total amount of solid content and content of each component with respect to this can be measured by well-known analytical means, such as liquid chromatography or gas chromatography, for example.

<Colorant (A)>

The coloring agent (A) may contain the dye (A1) and the pigment (A2) in addition to the compound (I).

The dye (A1) is not specifically limited, A well-known dye can be used, For example, a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned. Examples of the dye include compounds classified as having a color other than pigments in the color index (published by The Society of Dyers and Colorists), and known dyes described in the dyeing notes (color dyeing yarn). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, scrylium dyes, azo dyes Creidine dye, styryl dye, coumarin dye, quinoline dye, nitro dye, etc. are mentioned. Among these, organic solvent-soluble dyes are preferable.

Specifically, CI solvent yellow 4 (Hereinafter, description of CI solvent yellow is omitted, and description is made only of numbers.), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98. , 99, 117, 162, 163, 167, 189;

C.I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86,;

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

C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. C.I. solvent dyes,

CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 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;

CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76 , 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172 , 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281 , 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;

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

C.I. Acid Violet 6 B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45 , 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1 , 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147 , 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236 , 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340;

CI acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80 CI acid dyes such as , 104, 105, 106, 109,

CI Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 , 136, 138, 141;

CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 , 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

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

C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84 , 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153 , 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196 , 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246 , 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

C.I. direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;

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

C.I. Disperse Violet 26, 27;

C.I. Disperse dyes such as C.I. Disperse Blue 1, 14, 56, 60;

C.I. Basic Red 1, 9, 10;

CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66 , 67, 68, 81, 83, 88, 89;

C.I. Basic Violet 2;

C.I. basic green 1; C.I. basic dye such as;

C.I. reactive yellow 2, 76, 116;

C.I. Reactive Orange 16;

C.I. reactive red 36; C.I. reactive dyes such as

C.I. modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

CI Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

C.I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

CI Modern Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;

CI Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;

C.I. modern dyes such as C.I. Modern Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;

C.I. vat dyes, such as C.I. vat green 1, etc. are mentioned.

What is necessary is just to select these dyes suitably according to the spectral spectrum of a desired color filter.

It does not specifically limit as a pigment (A2), A well-known pigment can be used, For example, the pigment classified into the pigment by the color index (The Society of Dyers and Colorists publication) is mentioned.

As a pigment, it is CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, for example. , 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments;

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, 265 ;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 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, 58;

C.I. Brown pigments, such as Pigment Brown 23 and 25;

C.I. Black pigments, such as Pigment Black 1 and 7, etc. are mentioned.

As a pigment, C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; C.I. Violet pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38, are preferable, and C.I. Pigment Blue 15:3, 15:6 and C.I. Pigment violet 23 is more preferable, and C.I. Pigment blue 15:6 is more preferable. By including said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

If necessary, the pigment may be subjected to rosin treatment, surface treatment using a pigment derivative introduced with acidic or basic groups, etc., graft treatment to the pigment surface with a high molecular compound, etc., atomization treatment by sulfuric acid atomization method, etc., or to remove impurities Washing treatment with an organic solvent, water, etc., removal treatment by an ion exchange method of ionic impurities, etc. may be performed.

It is preferable that a pigment has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

As said pigment dispersant, surfactant, such as a cationic type, an anionic type, a nonionic type, an amphoteric type, a polyester type, a polyamine type, an acrylic type, etc. are mentioned, for example. These pigment dispersants may be used individually or in combination of 2 or more type. As the pigment dispersant, as a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Addisper (manufactured by CIBA), Ajinomoto Fine Techno Co., Ltd. product), Disperbyk (made by Big Chemi company), etc. are mentioned.

When using a pigment dispersant, the usage-amount becomes like this with respect to the total amount of a pigment (A2). Preferably they are 1 mass % or more and 100 mass % or less, More preferably, they are 5 mass % or more and 50 mass % or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

When the dye (A1) and the pigment (A2) are included, the content ratio (dye (A1)/pigment (A2)) of the dye (A1) and the pigment (A2) in the colorant (A) is based on mass, usually, It is 1/99 - 99/1, Preferably it is 3/97 - 40/60, More preferably, it is 5/95 - 30/70.

It is preferable that the content rate of compound (I) in a coloring agent (A) is 1-99 mass % with respect to the total amount of a coloring agent (A), More preferably, it is 30-90 mass %, More preferably, it is 40-80 mass %.

To [ the content rate of a coloring agent (A) ] with respect to the total amount of solid content, Preferably it is 5-60 mass %, More preferably, it is 7-55 mass %, More preferably, it is 9-50 mass %. When the content rate of the colorant (A) is within the above range, the color density when the color filter is used is sufficient, and the composition can contain a required amount of a resin and a polymerizable compound, so that a pattern having sufficient mechanical strength can be formed. .

<Resin (B)>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin. As resin (B), the following resins [K1] - [K6], etc. are mentioned.

Resin [K1]; A structural unit derived from at least one (a) (hereinafter sometimes referred to as “(a)”) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acids, and having 2 to 4 carbon atoms a copolymer having a structural unit derived from a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);

Resin [K2]; The structural unit derived from (a), the structural unit derived from (b), and the monomer (c) copolymerizable with (a) (however, it is different from (a) and (b)) ( a copolymer having a structural unit derived from "(c)" below;

Resin [K3]; A copolymer having a structural unit derived from (a) and a structural unit derived from (c);

Resin [K4]; A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (b) to the structural unit derived from (a);

Resin [K5]; A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b);

Resin [K6]; A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding carbonic anhydride.

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

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl tetra unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [ 2.2.1] Bicyclo unsaturated compounds containing a carboxy group, such as hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride; unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride;

Unsaturated mono[(meth)acryloyloxyalkyl] of polyvalent carbonic acid having a divalent or higher value, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] esters;

Unsaturated acrylates containing a hydroxyl group and a carboxy group in the same molecule, such as (alpha)-(hydroxymethyl)acrylic acid, etc. are mentioned.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility point to the aqueous alkali solution of resin obtained.

(b) has, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond polymerizable compound. As for (b), the monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations, such as "(meth)acryloyl" and "(meth)acrylate", also have the same meaning.

As (b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”), a monomer (b3) having a tetrahydropril group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”); and the like.

As (b1), for example, a monomer (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 hydrocarbon and a monomer (b1-2) having a structure in which hydrocarbons are epoxidized (hereinafter sometimes referred to as “(b1-2)”).

As (b1-1), glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) methyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene; 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. are mentioned. can

Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( meth)acrylate (eg, Cycloma A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cycloma M100; manufactured by Daicel Corporation) , the compound represented by the formula (BI), the compound represented by the formula (BII), etc. are mentioned.

[Formula 23]

[In formulas (BI) and (BII), 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 hydroxyl group.

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

R ^c represents a C1-C6 alkanediyl group.

* indicates a bond with O.]

As a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, etc. are mentioned.

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

As R ^a and R ^b , Preferably, a hydrogen atom, a methyl group, a hydroxymethyl group, 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned, More preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1 group. ,6-diyl group, etc. are mentioned.

As X ^a and X ^b , Preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O- are mentioned, More preferably, a single bond, *- CH ₂ CH ₂ -O- is mentioned (* represents a bond with O).

As a compound represented by Formula (BI), the compound etc. which are represented by any one of Formula (BI-1) - Formula (BI-15) are mentioned. Among them, formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) or formula (BI-11) - formula (BI-15) The compound represented by ) is preferable, and the compound represented by a formula (BI-1), a formula (BI-7), a formula (BI-9), or a formula (BI-15) is more preferable.

[Formula 24]

[Formula 25]

As a compound represented by Formula (BII), the compound etc. which are represented by any one of Formula (BII-1) - Formula (BII-15) are mentioned. Among them, formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) - formula (BII-15) ) is preferable, and the compound represented by a formula (BII-1), a formula (BII-7), a formula (BII-9), or a formula (BII-15) is more preferable.

[Formula 26]

[Formula 27]

The compound represented by Formula (BI) and the compound represented by Formula (BII) may be used individually, respectively, or may use 2 or more types together. When the compound represented by the formula (BI) and the compound represented by the formula (BII) are used together, these content ratios [the compound represented by the formula (BI): the compound represented by the formula (BII)] are on a molar basis, preferably 5: 95-95:5, More preferably, it is 20:80-80:20.

As (b2), the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

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

As (b), it is preferable that it is (b1) from the point which can make higher reliability, such as heat resistance of the color filter obtained and chemical-resistance. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, it is commonly referred to as “dicyclofentanyl (meth) acrylate” Also called "tricyclodecyl (meth) acrylate" in some cases), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (common name in the technical field) as "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) ) (meth)acrylic acid esters such as acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

Hydroxyl group-containing (meth)acrylic acid esters, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo[2.2.1]hepto-2-ene, 5-hydroxymethylbicyclo[2.2.1]hepto-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hepto-2 -ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1] hepto -2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hepto-2-ene,5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hepto- 2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-methyl Bicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] Hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] Hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] Hepto-2-ene, 5-phenoxycarbo nylbicyclo[2.2.1]hepto-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hepto-2-ene, 5,6-bis(cyclohexyloxycarbonyl) ) bicyclo unsaturated compounds such as bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl dicarbonylimide derivatives such as -6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1, 3-butadiene, etc. are mentioned.

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

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

Structural unit derived from (a); 2 to 60 mol%

Structural unit derived from (b); 40 to 98 mol%

It is preferable that

Structural unit derived from (a); 10-50 mol%

Structural unit derived from (b); 50 to 90 mol%

It is more preferable that

When the ratio of the structural unit of resin [K1] exists in said range, there exists a tendency excellent in the storage stability of colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance of the color filter obtained.

Resin [K1] is, for example, the method described in the document "Experimental Methods for Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd. Chemical Doujin 1st Edition 1st Edition Published March 1, 1972) and citations described in the document It can be prepared with reference to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, and heating and keeping warm while stirring how to do it In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, What is normally used in the said field|area can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2,2'- azobis (2,4-dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide, etc.) ) is mentioned, and what is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored curable resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent at the time of this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, so the colored curable resin 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 is among all the structural units constituting the resin [K2],

Structural unit derived from (a); 2-45 mol%

Structural unit derived from (b); 2-95 mol%

Structural unit derived from (c); 1-65 mol%

It is preferable that

Structural unit derived from (a); 5-40 mol%

Structural unit derived from (b); 5-80 mol%

Structural unit derived from (c); 5-60 mol%

It is more preferable that

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent tends to

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

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

Structural unit derived from (a); 2 to 60 mol%

Structural unit derived from (c); 40 to 98 mol%

It is preferable that

Structural unit derived from (a); 10-50 mol%

Structural unit derived from (c); 50 to 90 mol%

It is more preferable that

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

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

First, the copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as that of resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the said copolymer.

Continuing with the preparation of the copolymer of (a) and (c), the atmosphere in the flask is substituted from nitrogen to air, and (b), a reaction catalyst of carbonic acid or carbonic anhydride and a cyclic ether (e.g., tris(dimethyl Aminomethyl) phenol etc.) and a polymerization inhibitor (for example, hydroquinone etc.) etc. are put in a flask, For example, resin [K4] can be manufactured by 60-130 degreeC, and reacting for 1 to 10 hours. .

As for the usage-amount of (b), 5-80 mol is preferable with respect to 100 mol of (a), More preferably, it is 10-75 mol. By setting it as this range, there exists a tendency for the storage stability of colored curable resin composition, the developability at the time of forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the pattern obtained to become favorable. Since the reactivity of a cyclic ether is high and unreacted (b) is hard to remain|survive, as (b) used for resin [K4], (b1) is preferable and (b1-1) is preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (b), and (c).

Reaction conditions, such as a preparation method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the amount of heat generated by polymerization, etc.

Resin [K5] is a 1st step, it carries out similarly to the manufacturing method of resin [K1] mentioned above, and obtains the copolymer of (b) and (c). As for the copolymer obtained as described above, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a copolymer obtained as a solid (powder) by a method such as reprecipitation may be used.

The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer,

Structural unit derived from (b); 5-95 mol%

Structural unit derived from (c); 5-95 mol%

It is preferable that

Structural unit derived from (b); 10-90 mol%

Structural unit derived from (c); 10-90 mol%

It is more preferable that

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

It is preferable that the usage-amount of (a) made to react with said copolymer is 5-80 mol with respect to 100 mol of (b). Since the reactivity of a cyclic ether is high and unreacted (b) hardly remains, as (b) used for resin [K5], it is preferable that it is (b1), and it is further more preferable that it is (b1-1).

Resin [K6] is resin in which carboxylic acid anhydride was further reacted with resin [K5]. A hydroxy group generated by reaction of a cyclic ether with carbonic acid or carbonic anhydride is reacted with carbonic anhydride.

Examples of the carbonic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hepto-2-ene anhydride. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a).

Specifically as the resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth) Resin [K1] such as acrylic acid copolymer; (meth)acrylic acid/3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/vinyltoluene copolymer, glycidyl (meth)acrylate /benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylic Resin [K2], such as a rate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; Resin [K3] such as meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer; glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer Resin added, tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer with glycidyl (meth)acrylate added, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate Resin [K4], such as a resin obtained by adding glycidyl (meth) acrylate to / (meth) acrylic acid copolymer; to a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) ) Resin made by reacting acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer with (meth) acrylic acid, resins such as resin [K5]; tricyclodecyl (meth) ) Resin [K6], such as a resin which made tetrahydrophthalic anhydride react with resin which made (meth)acrylic acid react with the copolymer of acrylate/glycidyl (meth)acrylate, etc. are mentioned.

Especially, as resin (B), resin [K1] and resin [K2] are preferable, and resin [K2] is especially preferable.

Preferably the weight average molecular weight of polystyrene conversion of resin (B) is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. When molecular weight exists in said range, the hardness of a color filter improves, a residual film ratio is high, the solubility with respect to the developing solution of an unexposed part is favorable, and there exists a tendency for the resolution of a coloring pattern to improve.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of resin (B) is preferably 50-170 mg-KOH/g in conversion of solid content, More preferably, it is 60-150 mg-KOH/g, More preferably, it is 70-135 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

To [ the content rate of resin (B) ] with respect to the total amount of solid content, Preferably it is 7-65 mass %, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When the content rate of resin (B) exists in said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized with active radicals and/or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, etc., preferably Preferably, it is a (meth)acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate , propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa ( meth) acrylate and the like.

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

The weight average molecular weight of a polymeric compound (C) becomes like this. Preferably it is 150 or more and 2,900 or less, More preferably, they are 250 or more and 1,500 or less.

It is preferable that the content rate of a polymeric compound (C) is 7-65 mass % with respect to the total amount of solid content, More preferably, it is 13-60 mass %, More preferably, it is 17-55 mass %. When the content rate of a polymeric compound (C) exists in said range, there exists a tendency for the residual-film rate at the time of coloring pattern formation and the chemical-resistance of a color filter to improve.

<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, an acid, etc. under the action of light or heat, and a known polymerization initiator can be used. As a polymerization initiator which generate|occur|produces an active radical, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound are mentioned, for example.

The said O-acyl oxime compound is a compound which has a partial structure represented by Formula (d1). Hereinafter, * represents a bond.

[Formula 28]

　

Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanyl). Phenyl) octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[ 9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-a2-methyl-4-( 3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-( 2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carr bazol-3-yl]-3-cyclopentylpropan-1-one-2-imine; and the like. You may use commercial items, such as Irgacure OXE01, OXE02 (above, BASF company make), and N-1919 (made by ADEKA company). Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) At least one selected from the group consisting of octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine is preferable , N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine is more preferable. If it is these O-acyl oxime compounds, there exists a tendency for the color filter of high brightness to be obtained.

The said alkylphenone compound is a compound which has a partial structure represented by Formula (d2) or a partial structure represented by Formula (d3). Among these partial structures, the benzene ring may have a substituent.

[Formula 29]

　

　

As a compound which has a partial structure represented by Formula (d2), 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane- 1-on etc. are mentioned. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF company make).

As a compound which has a partial structure represented by Formula (d3), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- oligomers of on, α,α-diethoxyacetophenone, benzyl dimethyl ketal, and the like.

As an alkylphenone compound from a sensitivity point, the compound which has a partial structure represented by Formula (d2) is preferable.

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

2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound. You may use commercial items, such as Irgacua (trademark) 819 (made by BASF).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3). -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (For example, refer to Unexamined-Japanese-Patent No. 6-75372, Unexamined-Japanese-Patent No. 6-75373, etc.), 2 ,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5' -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 Application Laid-Open No. 62-174204, etc. ), an imidazole compound in which the phenyl group in the 1st position is substituted with a carboalkoxy group (see, for example, Japanese Patent Laid-Open No. 7-10913, etc.), etc. have.

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, and 4-phenyl Benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. Benzophenone compounds; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. can It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (especially amines) mentioned later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium-p- Toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p- Onium salts, such as toluenesulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

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

To [ content of a polymerization initiator (D) / 100 mass parts of total amounts of resin (B) and a polymeric compound (C)), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. When content of a polymerization initiator (D) exists in said range, since there exists a tendency for it to become highly sensitive and exposure time to shorten, productivity of a color filter improves.

<Polymerization initiation aid (D1)>

A polymerization initiation adjuvant (D1) is a compound used in order to accelerate|stimulate superposition|polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator, or a sensitizer. When a polymerization initiation adjuvant (D1) is included, it is used in combination with a polymerization initiator (D) normally.

Examples of the polymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carbonic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylamino 2-ethylhexyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as mihirazketone), 4,4'-bis(diethylamino)benzophenone, 4, 4'-bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, and 9,10- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxy. City oxantone etc. are mentioned.

Examples of the carbonic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chloro Phenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

When using these polymerization initiation adjuvant (D1), the content is with respect to 100 mass parts of total amounts of resin (B) and a polymeric compound (C), Preferably it is 0.1-30 mass parts, More preferably, it is 1-20 mass parts. is the mass part. When the amount of the polymerization initiation auxiliary (D1) is within this range, a coloring pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not specifically limited, The solvent normally used in this field|area can be used. For example, ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (containing OH in the molecule, - solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. These solvents may be used independently or may use 2 or more types together.

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, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

As the ether solvent, 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 monomethyl ether, propylene glycol monoethyl ether, 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, phenetol and methylanisole and the like.

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

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo pentanone, cyclohexanone, isophorone, and the like.

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

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

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

Among the above solvents, organic solvents having a boiling point of 120°C or more and 180°C or less at 1 atm are preferable from the viewpoint of coating properties and drying properties. Examples of the solvent include propylene glycol monomethyl ether acetate, N-methylpyrrolidone, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Ethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, N-methylpyrrolidone, and 4-hydroxy-4-methyl are preferable. -2-pentanone, propylene glycol monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate are more preferable.

To [ the content rate of a solvent (E) ] the total amount of the colored curable resin composition of this invention, Preferably it is 70-95 mass %, More preferably, it is 75-92 mass %. In other words, the total amount of solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When the content rate of the solvent (E) is within the above range, flatness at the time of application becomes favorable, and since color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Leveling agent (F)>

As a leveling agent (F), a silicone type surfactant, the silicone type surfactant etc. which have a silicone type surfactant, a fluorine type surfactant, and a fluorine atom are mentioned. These may have a polymerizable group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326 , KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint Stock Company), etc. can

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Florad (registered trademark) FC430, dong FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megapac (registered trademark) F142D, dong F171, dong F172, dong F173, dong F177, dong F183, dong F554, dong R30, RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EF303, copper EF351, copper EF352 (manufactured by Misbishi Material Electronics Chemical Co., Ltd.), Saffron (registered trademark) S381, copper S382, copper SC101, copper SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Refining Chemical Research Institute), and the like.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megapac (trademark) R08, Dong BL20, Dong F475, Dong F477, Dong F443 (DIC Co., Ltd. product), etc. are mentioned.

When containing a leveling agent (F), the content rate with respect to the total amount of colored curable resin composition, Preferably they are 0.001 mass % or more and 0.2 mass % or less, Preferably they are 0.002 mass % or more and 0.1 mass % or less, More preferably Preferably, it is 0.003 mass % or more and 0.05 mass % or less. In addition, the content rate of the said pigment dispersant is not included in this content rate. When the content rate of a leveling agent (F) exists in said range, the flatness of a color filter can be made favorable.

<Other ingredients>

The colored curable resin composition of this invention may contain well-known additives in this technical field, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, an optical stabilizer, and a chain transfer agent, as needed.

<Method for producing colored curable resin composition>

The colored curable resin composition of this invention is, for example, a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), and the solvent (E) used as needed, a leveling agent ( It can prepare by mixing F) and other components.

When using a pigment (A2), it is preferable to mix with a part or all of the solvent (E) beforehand, and to disperse|distribute using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix|blend a part or all of the said pigment dispersant and resin (B) as needed. The target colored curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid obtained in this way so that it may become a predetermined density|concentration.

The dye (A1) may be previously dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the said solution with a filter with a pore diameter of about 0.01-1 micrometer.

It is preferable to filter the colored curable resin composition after mixing with a filter with a hole diameter of about 0.01-10 micrometers.

<The manufacturing method of a color filter>

As a method of manufacturing a colored pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithography method is a method of apply|coating the said colored curable resin composition to a board|substrate, drying it, forming a coloring composition layer, exposing the said coloring composition layer through a photomask, and developing. In the photolithography method, the colored coating film which is the hardened|cured material of the said coloring composition layer can be formed by not using and/or developing a photomask at the time of exposure. Thus, the colored pattern and colored coating film which are coating-hardened|cured material of the colored curable resin composition of this invention formed can be used as the color filter of this invention.

The film thickness of the color filter to be produced is not specifically limited, It can adjust suitably according to the objective, a use, etc., For example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers. .

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, silicon-coated soda lime glass, or the like, a resin plate such as polycarbonate, polymethyl methacrylate or polyethylene terephthalate, silicon, or aluminum on the substrate , silver, silver/copper/palladium alloy thin films, etc. are used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on these board|substrates.

Formation of each color pixel by the photolithographic method can be performed with a well-known or customary apparatus and conditions. For example, it can be produced as follows.

First, a colored curable resin composition is apply|coated on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-baking) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained.

Examples of the coating method include a spin coating method, a slit coating method, a slit-and-spin coating method, and the like.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that they are 10 second - 60 minutes, and it is more preferable that they are 30 second - 30 minutes.

When performing reduced-pressure drying, it is preferable to carry out at the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

The film thickness of a coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

Next, the coloring composition layer is exposed through the photomask for forming the objective coloring pattern. The pattern on the said photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges, good to do Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate parallel rays to the entire exposure surface or to accurately align the photomask and the substrate on which the coloring composition layer is formed.

A coloring pattern is formed on a board|substrate by making a developing solution contact and developing the coloring composition layer after exposure. By image development, the unexposed part of a coloring composition layer melt|dissolves in a developing solution, and is removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Moreover, the developing solution may contain surfactant.

Any one of a paddle method, a dipping method, and a spray method may be sufficient as a developing method. Moreover, you may incline a board|substrate at an arbitrary angle at the time of development.

After image development, it is preferable to wash with water.

Moreover, it is preferable to post-baking to the obtained coloring pattern. 150-250 degreeC is preferable and, as for post-baking temperature, 160-235 degreeC is more preferable. 1 to 120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

According to the colored curable resin composition of this invention, the color filter excellent in chemical-resistance especially can be produced. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples from the beginning, and it is also carried out with appropriate changes within the range that can be suitable for the gist of the preceding and latter period. Of course, it is possible, and they are all included in the technical scope of the present invention.

In addition, in the following, unless otherwise indicated, "part" means "mass part" and "%" means "mass %".

In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; 1200 manufactured by Agilent, MASS; LC/MSD manufactured by Agilent).

[Synthesis Example 1]

[Formula 30]

　

To a flask equipped with a cooling tube and a stirring device, 10 parts of a dye (a neutralizing agent) represented by Formula (X), 50 parts of N-methylpyrrolidone, 9.0 parts of potassium carbonate, and 12.0 parts of 1-bromopropane are added to 90 The mixture was stirred at °C for 7 hours and a half. When the obtained reaction solution was added to 350 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals were precipitated. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60°C to obtain 8.0 parts of a compound represented by the formula (A-IM).

[Formula 31]

Identification of the compound represented by formula (A-IM)

(Mass spectrometry) Ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 819.2 and 739.5

Exact　Mass：　818.2 and 738.2

[Synthesis Example 2]

To a flask equipped with a cooling tube and a stirring device, 1 part of the compound represented by the formula (A-IM), 9.9 parts of distilled water, and 0.08 parts of sodium hydroxide are added, and an aqueous metal salt solution prepared from 4 parts of barium chloride dihydrate and 10 parts of distilled water under stirring 14 parts were dripped, and solid was deposited. The solid was separated by decantation, washed well with ion-exchanged water, dried under reduced pressure at 60°C, and the compound represented by formula (A-1) (a mixture of compound (I-359) and compound (I-360)) 0.7 got wealth

[Formula 32]

[Synthesis Examples 3 to 6]

A compound represented by formula (A-2) ( A mixture of compound (I-7) and compound (I-8)), a compound represented by formula (A-3) (a mixture of compound (I-95) and compound (I-96)), formula (A-4) A compound represented by (a mixture of compound (I-183) and compound (I-184)) and a compound represented by formula (A-5) (a mixture of compound (I-271) and compound (I-272)) were synthesized. .

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

[Synthesis Example 7]

[Formula 37]

Into a flask equipped with a cooling tube and a stirring device, 1 part of Pink Base (a chemical agent) represented by the formula (Y), 7 parts of N-methylpyrrolidone, 1.0 part of potassium carbonate, and 2.0 parts of ethyl 4-bromobutyrate In addition, it stirred at 100 degreeC for 7 hours and a half. After leaving to cool, 20 parts of 2N hydrochloric acid was added to the obtained reaction solution, extracted twice with 45 parts of chloroform, the chloroform layer was washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and it dried under reduced pressure at 60 degreeC, and obtained 4.1 parts of compounds represented by a formula (A-6-IM1).

[Formula 38]

Identification of the compound represented by formula (A-6-IM1)

(Mass spectrometry) Ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 803.5

Exact　Mass:　802.3

[Synthesis Example 8]

4.1 parts of compounds represented by Formula (A-6-IM1), 9.8 parts of methanol, and 3.5 parts of 8% sodium hydroxide aqueous solution were added to the flask provided with a cooling tube and a stirring apparatus, and it stirred at room temperature for 6 hours. The resulting reaction solution was added to 30 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60°C, and 1.0 parts of the compound (compound (Aa-75)) represented by the formula (A-6-IM2) was obtained.

[Formula 39]

Identification of the compound (compound (Aa-75)) represented by formula (A-6-IM2)

(Mass spectrometry) Ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 747.5

Exact　Mass：746.3

[Synthesis Example 9]

7 parts of compound (compound (Aa-75)) represented by formula (A-6-IM2), 61 parts of distilled water, and 0.82 part of sodium hydroxide are added to the flask provided with a cooling tube and a stirring apparatus, and barium chloride dihydrate is stirred under stirring. 26.55 parts of metal salt aqueous solution prepared from 7.55 parts and 19 parts of distilled water were dripped, and solid was deposited. The solid was separated by decantation, washed well with ion-exchanged water, and dried under reduced pressure at 60°C to obtain 5.8 parts of a compound (compound I-427) represented by the formula (A-6).

[Formula 40]

[Synthesis Example 10]

To a flask equipped with a cooling tube and a stirring device, 3 parts of Pink　Base represented by the formula (Y), 21 parts of N-methylpyrrolidone, and 1.7 parts of t-butoxypotassium were added and stirred at room temperature for 30 minutes. Then, 1.6 parts of 1-bromopropane was added, and it stirred at the same temperature for 1 hour. The resulting reaction solution was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 1 hour 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 3.0 parts of the compound represented by the formula (A-7-IM1).

[Formula 41]

Identification of the compound represented by formula (A-7-IM1)

(Mass spectrometry) Ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 617.5

Exact　Mass：　616.2

[Synthesis Example 11]

1 part of compound represented by Formula (A-7-IM1), 7 parts of N-methylpyrrolidone, 0.5 part of potassium carbonate, and 1.0 part of ethyl 4-bromobutyrate are added to the flask provided with a cooling tube and a stirring apparatus, and 100 degreeC was stirred for 5 and a half hours. The resulting reaction solution was added to 35 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60°C, and 1.2 parts of the compound represented by the formula (A-7-IM2) was obtained.

[Formula 42]

Identification of the compound represented by formula (A-7-IM2)

(Mass spectrometry) Ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 731.5

Exact　Mass：　730.3

[Synthesis Example 12]

1 part of the compound represented by Formula (A-7-IM2), 7 parts of methanol, and 2.7 parts of 8% sodium hydroxide aqueous solution were added to the flask provided with a cooling tube and a stirring apparatus, and it stirred at room temperature for 3 and a half hours. The resulting reaction solution was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60°C, and 0.9 parts of the compound (compound (Aa-36)) represented by the formula (A-7-IM3) was obtained.

[Formula 43]

Identification of the compound (compound (Aa-36)) represented by formula (A-7-IM3)

(Mass spectrometry) Ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 703.5

Exact　Mass：　702.3

[Synthesis Example 13]

5 parts of compound (compound (Aa-36)) represented by formula (A-7-IM3), 5 parts of methanol, 62 parts of distilled water, and 0.31 part of sodium hydroxide are added to the flask provided with a cooling tube and a stirring apparatus, and stirring 7.50 parts of a metal salt aqueous solution prepared from 1.92 parts of barium chloride dihydrate and 5.58 parts of distilled water was added dropwise to precipitate solid. The solid was separated by decantation, washed well with ion-exchanged water, and dried under reduced pressure at 60°C to obtain 5.1 parts of the compound (compound (I-388)) represented by the formula (A-7).

[Formula 44]

[Synthesis Example 14]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, 305 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 70° C. while stirring. Next, 60 parts of acrylic acid, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1) are 50 : Mix at 50.) 440 parts were melt|dissolved in 140 parts of propylene glycol monomethyl ether acetate, the solution was prepared, and the said solution was dripped in the flask kept at 70 degreeC over 4 hours using the dropping funnel.

[Formula 45]

On the other hand, a solution obtained by dissolving 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was dripped into the flask over 4 hours using another dropping funnel. . After the dropwise addition of the polymerization initiator solution was completed, the temperature was maintained at 70° C. for 4 hours, and then cooled to room temperature, the weight average molecular weight (Mw) was 9.1×10 ³ , molecular weight distribution was 2.16, solid content 34.8%, solid content The converted acid value obtained the resin B1 solution of 81 mg-KOH/g. Resin B1 has a structural unit shown below.

[Formula 46]

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of resin obtained by the synthesis example 14 was performed on condition of the following using GPC method.

Apparatus; K2479 (manufactured by Shimadzu Corporation)

Column：SHIMADZU　Shim-pack　GPC-80M

Column temperature; 40°C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL/min

detector; RI

Standard material for calibration　;TSK　STANDARD　POLYSTYRENE　F-40, F-4, F-288, A-2500, A-500 (manufactured by Toso Corporation)

Ratio (Mw/Mn) of the polystyrene conversion weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution.

Examples 1 to 7, Comparative Example 1

(Preparation of colored curable resin composition)

Each component was mixed with the following composition, and colored curable resin composition was obtained.

[Table 9]

In Table 9, each component shows the following compounds.

(A-1): The compound represented by Formula (A-1)

(A-2): The compound represented by Formula (A-2)

(A-3): The compound represented by Formula (A-3)

(A-4): The compound represented by a formula (A-4)

(A-5): The compound represented by Formula (A-5)

(A-6): The compound represented by Formula (A-6)

(A-7): The compound represented by Formula (A-7)

(A-x): A mixture of compounds represented by the following formula

[Formula 47]

(B-1): Resin B1 (solid content conversion)

(C-1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (irgacure (registered trademark) OXE 01; manufactured by BASF)

(E-1): N-methylpyrrolidone

(E-2): Propylene glycol monomethyl ether acetate

(F-1): Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.)

<Production of the coloring pattern>

After apply|coating a colored curable resin composition by the spin coating method on the glass substrate (Eagle 2000; Corning company make) of 5 cm corner, it prebaked at 100 degreeC for 3 minutes, and the coloring composition layer was obtained. After cooling, the interval between the substrate on which the coloring composition layer was formed and the quartz glass photomask was set to 100 µm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an atmospheric atmosphere, and an exposure amount of 150 mJ/cm 2 (based on 365 nm) ) was irradiated with light. As a photomask, the thing in which the 100 micrometers line-and-space pattern was formed was used. The coloring composition layer after light irradiation was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, and after washing with water, post-baking at 230°C for 20 minutes in an oven and a coloring pattern was obtained.

<Measurement of film thickness>

About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 10.

<Evaluation of chemical resistance>

About the obtained coloring pattern, the spectroscopy is measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd. product), and the xy chromaticity coordinate (x, y) in the XYZ color space system of CIE using the characteristic function of C light source. ) and the stimulus value Y were measured. The obtained coloring pattern was immersed in N-methylpyrrolidone at 50 degreeC for 30 minute(s). After immersion, xy chromaticity coordinates (x, y) and Y were measured in the same manner as before immersion, and the color difference Eab* was calculated from the measured values by the method described in JIS Z 830: 2009 (7. Calculation method of color difference). On the basis of Eab* of the colored curable composition obtained in Comparative Example 1, the improvement rate of chemical resistance was calculated according to the following formula. A result is shown in Table 10.

Improvement rate (%) of Example k = a (Eab* of Comparative Example 1 - Eab* of Example k)/Eab*｝×100　　　 of Comparative Example 1 (where k represents an integer of 1 to 7)

[Table 10]

According to the colored curable resin composition of an Example, it was confirmed that the obtained coloring pattern was excellent in chemical-resistance. From this, it turns out that the colored coating film and colored pattern obtained from the colored curable resin composition of this invention are excellent in chemical-resistance.

According to the colored curable resin composition of this invention, the color filter which has favorable chemical-resistance can be formed. The color filter is useful as a color filter used for a display device (eg, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a solid-state image sensor.

Claims (5)

a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
Colored curable resin composition in which the said coloring agent (A) contains the compound represented by Formula (Ia-2).

[In formula (Ia-2), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the monovalent saturated hydrocarbon group of ^{R 31} and R ^{32 is,} -SO ₃ ^- , -COO ^- , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom may be substituted, and the hydrogen atom contained in the monovalent aromatic hydrocarbon group is -SO ₃ ^- , -COO ^- or C 1 It may be substituted with the alkoxy group of ~3, and _{-CH 2} - contained in the monovalent saturated hydrocarbon group of ^{R 31} and R ³² may be substituted with -O-, -CO- or -NR ^{11 -.}
R ³³ and R ³⁴ each independently represent -SO ₃ ^- , -COO ^- , 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.
R ³¹ and R ³³ may be taken together to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be taken together to form a ring containing a nitrogen atom.
p1 and p2 each independently represent the integer of 0-5. When p1 is 2 or more, a plurality of R ³³ may be the same or different, and when p2 is 2 or more, a plurality of R ³⁴ may be same or different.
R ¹¹ 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.
Mr ⁺ represents a manganese ion or an iron (III) ion.
k represents the integer of 1-3. q represents an integer greater than or equal to 1; r represents an integer of 2 or more. n represents an integer of 1 or more. However, k, q, n, and r satisfy k×q=n×r.] delete The method according to claim 1,
Colored curable resin composition which does not contain a dispersing agent different from resin (B). The color filter which is an application|coating hardened|cured material of the colored curable resin composition of Claim 1. A display device comprising the color filter of claim 4 .