JP2013203955A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition capable of forming a high-contrast color filter.SOLUTION: A colored curable composition includes: a coloring agent; a resin; a polymerizable compound; a polymerization initiator; and a compound represented by formula (Q1). The coloring agent is a coloring agent including xyanthene dye, the content of the coloring agent is 5-60 mass% relative to the total amount of the solid content. In formula (Q1), Aand Aeach independently represent hydrogen atom or 1-8C hydrocarbon group. A, A, Aand Aeach independently represent hydrogen atom or 1-8C hydrocarbon group, or Aand Amay form a benzene ring together with carbon atoms to which these are bonded.

Description

  The present invention relates to a colored curable resin composition.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a colored curable resin composition, a colored curable resin composition comprising a dye, a pigment, a resin, a polymerizable compound, a polymerization initiator, and a solvent is known (Patent Document 1).

JP 2010-32999 A

  Conventionally known colored curable resin compositions described above have not always been sufficiently satisfactory in the contrast of the color filter obtained from the colored curable resin composition.

［式（Ｑ１）中、Ａ^１及びＡ^２は、互いに独立に、水素原子又は炭素数１〜８の炭化水素基を表す。
Ａ^３、Ａ^４、Ａ^５及びＡ^６は、互いに独立に、水素原子又は炭素数１〜８の炭化水素基を表すか、Ａ^３及びＡ^４は、一緒になってこれらが結合する炭素原子とともにベンゼン環を形成してもよい。］
［２］ 着色剤が、さらに顔料を含む着色剤である［１］記載の着色硬化性樹脂組成物。
［３］ ［１］又は［２］記載の着色硬化性樹脂組成物により形成されるカラーフィルタ。
［４］ ［３］記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A colorant, a resin, a polymerizable compound, a polymerization initiator, and a compound represented by the formula (Q1),
The colorant is a colorant containing a xanthene dye,
Colored curable resin composition whose content of a coloring agent is 5 to 60 mass% with respect to the total amount of solid content.

[In Formula (Q1), A ¹ and A ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
A ³ , A ⁴ , A ⁵ and A ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or A ³ and A ⁴ are carbon atoms to which they are bonded together. A benzene ring may be formed together. ]
[2] The colored curable resin composition according to [1], wherein the colorant further includes a pigment.
[3] A color filter formed from the colored curable resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

  According to the colored curable resin composition of the present invention, a high-contrast color filter can be formed.

It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention.

The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a compound represented by the formula (Q1) (hereinafter referred to as “compound ( Q1) ”may be included.
The colorant (A) contains a xanthene dye (A1).
The colorant (A) preferably contains a pigment (A2).
The colored curable resin composition of the present invention preferably further contains a solvent (E) and / or a leveling agent (F).
The colored curable resin composition of the present invention may contain a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colorant (A) preferably contains a xanthene dye (A1) and further contains a pigment (A2).
The xanthene dye (A1) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (A1) include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. Others are also the same), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like. Among these, those that are soluble in an organic solvent are preferable.

  Among these, as the xanthene dye (A1), a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When using a compound (1a), content of the compound (1a) in a xanthene dye (A1) becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (A1).

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、互いに独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。Ｒ¹及びＲ^２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂ ^-、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上のとき、複数のＲ⁵は互いに同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘ⁻は、ハロゲン化物イオン又は有機金属アニオンを表す。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表し、４つのＲ¹¹は互いに同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよく、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−で置き換っていてもよい。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子、又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］

[In Formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR ¹¹ —. Also good. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 -, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R ⁸ or —SO ₂ NR ⁹ R ¹⁰ is represented.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same as or different from each other.
a represents an integer of 0 or 1.
X ⁻ represents a halide ion or an organometallic anion.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and the four R ^{11 s} may be the same as or different from each other.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group, and the saturated hydrocarbon group -CH ₂ contained in - may have I replace by -O-.
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 contained in the saturated hydrocarbon group ₂ - is -O -, - CO -, - NH- or -NR ⁸ - may have I placed conversion in, R ⁹ and R ^10, 3-10 membered ring containing a nitrogen atom bonded to each other The heterocyclic ring may be formed.
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. ]

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.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - CO ₂ H, —CO ₂ R ⁸ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and preferably _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, the colored curable resin composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in 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, and a heptyl group. Linear alkyl groups such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned.
The hydrogen atom contained in the saturated hydrocarbon group in R ^{1 to} R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
The hydrogen atom contained in the saturated hydrocarbon group in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxy group or a halogen atom.

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

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group.

Examples of —CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, 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-butylsulfamoyl 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 N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.

R ^{5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H or _SO 2 NHR ⁹ are preferred, SO ₃ ^{-, _{-SO 3 - Z +, -SO 3}} H or _SO 2 NHR ⁹ is more preferable.
m is preferably 1 to 4, and more preferably 1 or 2.

The alkyl group having 1 to 6 carbon atoms in R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms in 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 .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), when R ¹¹ is any of these groups, the color filter having less foreign matter from the colored curable resin composition of the present invention containing the compound (1a) Can be formed.

Examples of the X ⁻ halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion.

The organometallic anion X ⁻ has a structure in which a metal atom capable of forming a divalent or higher valent metal ion and an organic compound are bonded by an ionic bond or a coordinate bond.
Examples of the organic compound include a salicylic acid which may have a substituent, a compound having a plurality of carboxymethyl groups bonded to an amino group, a benzylic acid which may have a substituent, and a substituent. Examples thereof include good mandelic acid and picolinic acid optionally having a substituent. The organometallic anion is preferably an organometallic anion having a structure derived from a salicylic acid which may have a substituent or a compound having a plurality of carboxymethyl groups bonded to an amino group.

  Examples of the salicylic acid optionally having the above substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, and 3-methoxysalicylic acid. 2-hydroxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichloro Salicylic acid, 4-hydroxysalicylic acid, 5-hydroxysalicylic acid and the like can be mentioned.

Examples of the compound having a plurality of carboxymethyl groups bonded to the amino group include the following compounds.

Examples of the benzylic acid optionally having the above substituent include the following compounds.

Examples of the mandelic acid optionally having the above substituent include the following compounds.

Examples of the picolinic acid which may have the above substituent include the following compounds.

Examples of the metal atom capable of forming a divalent or higher metal ion include Al, Cr, Co, Fe, Cu, Ni, Co, Zn, Mg, Ca, and Ba.
Of these, Al, Cr and Co are preferable.

（式中、ＬはＡｌ又はＣｒを表す。） As the organometallic anion, an anion represented by the formula (XA) is preferable.

(In the formula, L represents Al or Cr.)

  As the compound (1a), a compound represented by the formula (2a), the formula (3a) or the formula (4a) (hereinafter referred to as “compound (2a)”, “compound (3a)”, “compound (4a)”, respectively) There is a). These may be tautomers thereof.

［式（２ａ）中、Ｒ²¹〜Ｒ²⁴は、互いに独立に、水素原子、−Ｒ²⁶又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表す。Ｒ²¹及びＲ²²は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²³及びＲ²⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ²⁵は、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ１⁺又は−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ１は、０〜５の整数を表す。ｍ１が２以上のとき、複数のＲ²⁵は互いに同一でも異なってもよい。
ａ１は、０又は１の整数を表す。
Ｘ１⁻は、ハロゲン化物イオンを表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ１⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺又はＫ⁺を表し、４つのＲ²⁷は互いに同一でも異なってもよい。
Ｒ²⁷は、炭素数１〜２０の１価の飽和炭化水素基又はベンジル基を表す。］

[In Formula (2a), 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 ²¹ and R ²² may together form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may together form a ring containing a nitrogen atom.
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents the integer of 0-5. When m1 is 2 or more, the plurality of R ²⁵ may be the same as or different from each other.
a1 represents an integer of 0 or 1.
X1 ^- represents a halide ion.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and the four R ^{27 s} may be the same as or different from each other.
R ²⁷ represents a monovalent saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ include the same groups as those mentioned as the aromatic hydrocarbon group for R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of R ^{21 to} R ²⁴ , 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 aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferred 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 hydrogen contained in the aromatic hydrocarbon group atom, -SO ₃ ^- in which are substituted with Z1 ⁺ or -SO ₂ NHR ^26. When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (2a).

As a ring containing a nitrogen atom formed by R ²¹ and R ²² together and a ring containing a nitrogen atom formed by R ²³ and R ²⁴ together, R ¹ and R ² are combined. The thing similar to the ring to form is mentioned. Among these, an aliphatic heterocyclic ring is preferable. Examples of the aliphatic heterocycle include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
When R ²¹ to R ²⁴ is ^{-R 26,} -R ²⁶ each independently is preferably a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When R ²⁶ is these groups, a color filter with less generation of foreign matters can be formed from the colored curable resin composition of the present invention containing the compound (2a).

Z1 ⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ .
As the ⁺ N (R ²⁷ ) ₄ , at least two of the four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), when R ²⁷ is any of these groups, the occurrence of foreign matters is less from the colored curable resin composition of the present invention containing the compound (2a). A color filter can be formed.

  m1 is preferably 1 to 4, and more preferably 1 or 2.

［式（３ａ）中、Ｒ³¹及びＲ³²は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ³³及びＲ³⁴は、互いに独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基又は炭素数１〜４のアルキルスルホニル基を表す。
Ｒ³¹及びＲ³³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ³²及びＲ³⁴は、一緒になって窒素原子を含む環を形成してもよい。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上のとき、複数のＲ³³は互いに同一でも異なってもよく、ｑが２以上のとき、複数のＲ³⁴は互いに同一でも異なってもよい。
Ｒ^１１は、上記と同じ意味を表す。］

[In the formula (3a), R ³¹ and R ³² independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group has 6 to 6 carbon atoms. May be substituted with 10 aromatic hydrocarbon groups or a halogen atom, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkoxy group having 1 to 3 carbon atoms, —CH ₂ — contained in the hydrogen group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ^<33> and R ^<34 > represent a C1-C4 alkyl group, a C1-C4 alkylsulfanyl group, or a C1-C4 alkylsulfonyl group mutually independently.
R ³¹ and R ³³ may be combined to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be combined to form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ³³ may be the same or different, and when q is 2 or more, the plurality of R ³⁴ may be the same or different.
R ¹¹ represents the same meaning as described above. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ³² include those having 1 to 10 carbon atoms among those in R ⁸ .
Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent 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.
R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in 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.
The alkylsulfonyl group of 1 to 4 carbon atoms in R ³³ and R ^34, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, a butyl sulfonyl group and isopropylsulfonyl group.
R ³³ and R ³⁴ are preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.

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

［式（４ａ）中、Ｒ⁴¹〜Ｒ⁴⁴は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｒ⁴⁵は、−ＣＯ_２ ^-、−ＣＯ_２Ｈ又は−ＣＯ_２Ｒ⁴⁶を表す。
ｍ２は、０〜５の整数を表す。ｍ２が２以上のとき、複数のＲ⁴⁵は互いに同一でも異なってもよい。
ａ２は、０又は１の整数を表す。
Ｘ２⁻は、有機金属アニオンを表す。
Ｒ⁴⁶は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子又はヒドロキシ基で置換されていてもよく、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−で置き換っていてもよい。］
Ｘ２⁻の有機金属アニオンとしては、Ｘ⁻の有機金属アニオンと同様のものが挙げられる。

[In the formula (4a), R ^{41 to} R ⁴⁴ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ⁴⁵ represents —CO ₂ ⁻ , —CO ₂ H or —CO ₂ R ⁴⁶ .
m2 represents an integer of 0 to 5. When m2 is 2 or more, the plurality of R ⁴⁵ may be the same as or different from each other.
a2 represents an integer of 0 or 1.
X2 ^- represents an organometallic anion.
R ⁴⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom or a hydroxy group, and the saturated hydrocarbon group -CH ₂ contained in - may have I replace by -O-. ]
X2 ^- The organometallic anions, X ^- is the same as those described organometallic anion.

Examples of compound (1a) include compounds represented by formula (1-1) to formula (1-47). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group.

Among the above compounds, the compounds represented by the formula (1-1) to the formula (1-23) or the formula (1-37) to the formula (1-43) correspond to the compound (2a), and the formula (1- The compound represented by any one of 24) to formula (1-36) corresponds to the compound (3a), and the compound represented by any one of formulas (1-44) to (1-47) is the compound ( This corresponds to 4a).
Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).
Moreover, the compound represented by Formula (1-24)-Formula (1-33), Formula (1-46), or Formula (1-47) is also preferable at the point which is excellent in the solubility to an organic solvent.

  As the xanthene dye (A1), a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industries, Ltd.) may be used. it can. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

The pigment (A2) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI 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 CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  Examples of the pigment include C.I. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Violet 23 is more preferable, and C.I. I. Pigment Blue 15: 6 is more preferable. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  The colorant (A) may further contain a dye different from the xanthene dye (A1) (hereinafter sometimes referred to as “other dye”). As other dyes, known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Other dyes include, for example, compounds classified as having a hue other than pigment in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (Color Dyeing) Is mentioned. Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes.

  The content of the xanthene dye (A1) is preferably 1 to 99% by mass, more preferably 1 to 50% by mass, and further preferably 1 to 30% by mass with respect to the total amount of the colorant (A). It is.

  Content of a coloring agent (A) is 5-60 mass% with respect to the total amount of solid content, Preferably it is 8-55 mass%, More preferably, it is 10-50 mass%. When the content of the colorant (A) is in the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a pattern with sufficient mechanical strength can be formed. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Is more preferable. Examples of such resins include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a copolymer of a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is 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-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) 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- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), and Formula (II) The compound etc. which are represented by these are mentioned.

[In Formula (I) and Formula (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -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.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I-15) A compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

  The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination with the compound represented by formula (I) and the compound represented by formula (II). May be. When these are used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 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 this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy 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, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. Tend.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 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 when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the proportion of structural units derived from each of 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); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is respectively based on 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 to 90 mol%
It is more preferable that

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; 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 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Resin such as acrylic acid copolymer [K3]; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / styrene / (meta ) Resin with glycidyl (meth) acrylate added to acrylic acid copolymer, glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer Resins such as resin [K4]; tricyclodecyl (meth) acrylate / glycidyl (meta Resins such as a resin obtained by reacting an acrylate copolymer with (meth) acrylic acid, a resin obtained by reacting a tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate copolymer with (meth) acrylic acid [K5]; a resin such as a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride [K6] Etc.
Especially, as resin (B), resin [K1] and resin [K2] are preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

  Content of resin (B) becomes like this. Preferably it 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 of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 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, etc. Is mentioned.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and O-acyloxy compounds. More preferred is a polymerization initiator containing a sulfur compound.

前記Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。これらのＯ−アシルオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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- {2-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-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 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] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  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-methoxy Styryl) -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-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

  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 (see, for example, JP-A-6-75372 and JP-A-6-75373), 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 (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913).

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

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

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

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

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

［式（Ｑ１）中、Ａ^１及びＡ^２は、互いに独立に、水素原子又は炭素数１〜８の炭化水素基を表す。
Ａ^３、Ａ^４、Ａ^５及びＡ^６は、互いに独立に、水素原子又は炭素数１〜８の炭化水素基を表すか、Ａ^３及びＡ^４は、一緒になってこれらが結合する炭素原子とともにベンゼン環を形成してもよい。］ <Compound (Q1)>
Compound (Q1) is represented by formula (Q1).

[In Formula (Q1), A ¹ and A ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
A ³ , A ⁴ , A ⁵ and A ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or A ³ and A ⁴ are carbon atoms to which they are bonded together. A benzene ring may be formed together. ]

Examples of the hydrocarbon group of A ^{1 to} A ⁶ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Alkyl groups such as 1,1-dimethylbutyl group and 1,1,3,3-tetramethylbutyl group.

［式（Ｑ１−１）中、Ａ^１及びＡ^２は、前記と同義である。
Ａ^１１〜Ａ^１４は、互いに独立に、水素原子又は炭素数１〜８の炭化水素基を表す。］

［式（Ｑ１−２）中、Ａ^１及びＡ^２は、前記と同義である。
Ａ^１５及びＡ^１６は、互いに独立に、水素原子又は炭素数１〜８の炭化水素基を表す。］ As the compound (Q1), a compound represented by the formula (Q1-1) or the formula (Q1-2) can be given.

[In the formula (Q1-1), A ¹ and A ² are as defined above.
A < ¹¹ > -A < ¹⁴ > represents a hydrogen atom or a C1-C8 hydrocarbon group mutually independently. ]

[In the formula (Q1-2), A ¹ and A ² are as defined above.
A ¹⁵ and A ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. ]

Examples of the compound represented by the formula (Q1-1) include hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, p-methoxyphenol, 4-pentyloxyphenol, and 4-hydroxy-3. -Tert-butylanisole, 4-butoxyphenol, 2,5-bis (1,1-dimethylbutyl) -4-methoxyphenol, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, etc. Is mentioned.
Examples of the compound represented by the formula (Q1-2) include 1,4-dihydroxynaphthalene, 1-hydroxy-4-methoxynaphthalene, 1,4-dimethoxynaphthalene, and the like.
As the compound (Q1), compounds described in JP2011-209594A can also be used.
As the compound (Q1), a compound represented by the formula (Q1-2) is preferable.

  The content of the compound (Q1) is preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 10% by mass or less with respect to the total amount of solids. When the content of the compound (Q1) is within this range, a high-contrast color filter can be obtained.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, 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 and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

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

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

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

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

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

  Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of the colored curable resin composition of this invention, More preferably, it is 75-92 mass%. In other words, the total amount of the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the colored composition layer formed by applying to the substrate and then drying tends to have excellent flatness, so that a color filter with less unevenness is produced. In addition, a color filter having a sufficient color density can be manufactured. .

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by 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 (made by Momentive Performance Materials Japan GK) Can be mentioned.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, and preferably 0.002% by mass to 0.1%, based on the total amount of the colored curable resin composition. It is not more than mass%, more preferably not less than 0.005 mass% and not more than 0.05 mass%. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention is used, for example, as a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a compound (Q1), and as necessary. It can be prepared by mixing the solvent (E), the leveling agent (F), the polymerization initiation assistant (D1) and other components.
When the pigment (A2) is included, the pigment is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The xanthene dye (A1) may be previously dissolved in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter and liquid crystal display device>
Examples of the method for forming a color filter with the colored curable resin composition of the present invention include a photolithographic method and a method using an inkjet device. Photolithographic methods include, for example, applying the colored curable resin composition of the present invention onto a substrate, removing volatile components such as a solvent and drying to form a colored composition layer, and passing through a photomask. Then, the coloring composition layer is exposed and developed. After development, a colored pattern can be formed by heating as necessary. In the colored pattern forming method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus obtained can be used as a color filter.
As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.
The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the intended use and the like, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, more preferably 1 to 6 μm. .

Next, a method for forming a pattern on a glass substrate on which a thin film transistor (hereinafter referred to as “TFT”) is formed will be described.
Specifically, a plurality of TFTs 22 are formed for each pixel on the glass substrate 21 by a known method such as a photolithography technique (see FIG. 1). The TFT 22 is formed of, for example, molybdenum (Mo) on the glass substrate 21 and constitutes part of the gate line, and, for example, a nitride film (SiN _x ) and an oxide film formed on the gate electrode 22a. A gate insulating film 22b made of a laminated film of (SiO ₂ ), a polycrystalline silicon film 22c formed on the gate insulating film 22b, and a laminated film of an oxide film (SiO ₂ ) and a nitride film (SiN _x ), for example. The protective film 22d is formed of a film. A region facing the gate electrode 22a of the polycrystalline silicon film 22c is a channel region of the TFT 22, and regions on both sides of the channel region are a source region or a drain region. The source region of the polycrystalline silicon film 22c is electrically connected to a signal line 27 made of, for example, aluminum (Al) through a connection hole (contact hole) provided in the protective film 22d. The drain region of the polycrystalline silicon film 22c is electrically connected to the pixel electrode 24 through a connection hole (contact hole) 201 as will be described later.

  When forming a plurality of TFTs 22 on the glass substrate 21 for each pixel, an alignment mark (not shown) is formed on the glass substrate 21 simultaneously with the TFTs 22. As will be described later, this alignment mark serves as a reference for alignment in the formation process of the color filter layer 23. These alignment marks can also be used as marks serving as a reference for bonding the drive substrate and the counter substrate. The alignment mark can be formed in the same process using at least one layer when forming a metal layer such as wiring or a polycrystalline silicon layer in the manufacturing process of the TFT 22.

Next, the colored curable resin composition of the present invention is applied on the glass substrate 21 on which the TFT 22 and the alignment mark are formed, and volatile components such as a solvent are removed by drying by heating (prebaking) and / or drying under reduced pressure. And dried to form a colored composition layer having a thickness of 0.5 to 5.0 μm, for example, 1.0 μm.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 60-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

Next, the colored composition layer is irradiated with ultraviolet rays through a photomask (not shown), and unnecessary portions are selectively removed with a developer to reach the drain region of the polycrystalline silicon film 22c. After obtaining the colored composition layer formed in the pixel in which the connection hole (contact hole) 201 is formed, it is washed with water.
By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.

  Thereafter, in order to reflow (reflow) the colored composition layer in which the connection hole (contact hole) 201 is formed and / or to cure the polymerizable compound or the like contained in the colored composition layer, for example, 100 to Heating is performed at a temperature of 300 ° C., preferably 150 to 230 ° C., for example for 1 to 120 minutes, preferably for 10 to 60 minutes. Thus, a colored curable resin composition layer 23A that is a colored pattern is formed. This colored curable resin composition layer 23A corresponds to the color filter of the present invention.

  By repeating this operation, the colored curable resin composition layer 23A is formed from the red colored curable resin composition, the green colored curable resin composition, and the blue colored curable resin composition, respectively, thereby corresponding to each pixel column. Thus, the color filter layer 23 including the red filter 23a, the green filter 23b, and the blue filter 23c is formed (see FIG. 2). A region between the filters of the color filter layer 23 is a mixed region of adjacent colors. Since this region is a light-shielding region facing the signal line 27, there is no particular problem in quality. Note that the region between the filters may not be colored.

  Subsequently, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 μm, for example, is formed so as to cover the color filter layer 23 by, for example, a spin coating method. Next, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and the regions corresponding to the connection holes 201 and unnecessary portions are selectively removed with a developer, thereby polycrystal After a connection hole (contact hole) 202 reaching the drain region of the silicon film 22c is formed, it is washed with water. Thereafter, in order to reflow (reflow) the photosensitive resin film 29, heating is performed at a temperature in the range of 100 to 300 ° C., for example, 200 ° C. Next, in order to remove residues such as dyes and organic substances deposited in the contact hole 202, etching with oxygen plasma is performed, and further, for example, etching with dilute hydrofluoric acid is performed to remove the oxide film formed by oxygen plasma. To do.

  Next, a transparent conductive material, for example, ITO (Indium-Tin Oxide) is formed on the photosensitive resin film 29 by sputtering, for example, and this ITO film is formed by photolithography and etching. Patterning is performed to form a transparent pixel electrode 24 (see FIG. 3). The pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on a device to be manufactured. After that, after forming an alignment film by a known method, a liquid crystal display device can be manufactured by bonding the drive substrate and the counter substrate.

  According to the colored curable resin composition of the present invention, a color filter particularly excellent in contrast can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.
Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.
In the following synthesis examples, the compounds were identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type) or elemental analysis (VARIO-EL; (Elemental Co., Ltd.)).

[Synthesis Example 1]
Gradually 7.83 parts of 2- (4-diethylamino-2-hydroxybenzoyl) benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) in 50 parts of 98% sulfuric acid so that the temperature of the mixture is 30 ° C. or lower during mixing. And mixed. The obtained solution was cooled to 5 ° C., and 5.37 parts of 3- (isopropylamino) phenol (manufactured according to the method described in JP-A-9-169708) was added thereto. The mixture was then stirred at 5 ° C. for 65 hours. The reaction mixture was added to 250 parts of ice water, and the precipitate was obtained by suction filtration. The residue was dissolved in 180 parts of chloroform, 300 parts of ion exchange water was added, and the aqueous layer was adjusted to pH 10 with a 10% aqueous sodium hydroxide solution and stirred for 1 hour. The chloroform layer was separated, washed with 200 parts of ion exchange water and dehydrated with magnesium sulfate. Chloroform was distilled off from the solution obtained by removing magnesium sulfate under reduced pressure to obtain 5.50 parts of a compound represented by the formula (hx).

  3.00 parts of a compound represented by the formula (hx), 3.16 parts of triethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.24 part of dimethylaminopyridine (manufactured by Wako Pure Chemical Industries, Ltd.), 30 parts of dehydrated chloroform was added to 0.18 part of 1S)-(+)-10-camphorsulfonic acid (manufactured by Kanto Chemical Co., Inc.), and the mixture was stirred at room temperature for 1 hour. A solution prepared by dissolving 1.83 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Dojin Chemical Laboratory Co., Ltd.) in 7.2 parts of dehydrated chloroform so as not to exceed 30 ° C. The solution was added dropwise and stirred at room temperature for 5 hours. The chloroform solution was separated with 300 parts of 1N hydrochloric acid and then with 200 parts of 10% brine and dehydrated with magnesium sulfate. Chloroform was distilled off from the solution obtained by removing magnesium sulfate under reduced pressure to obtain 3.59 parts of a compound represented by the formula (hy).

A solution (s1) in which 1.50 parts of a compound represented by the formula (hz) (BONTRON (registered trademark) E-108, manufactured by Orient Chemical Industry Co., Ltd.) is dissolved in 120 parts of N, N-dimethylformamide. It was created. Separately, a solution (t1) was prepared by dissolving 1.79 parts of the compound represented by the formula (hy) in 100 parts of N, N-dimethylformamide. The solution (t1) was added to the solution (s1) at 25 ° C., and then the temperature was raised to 80 ° C. and stirred for 6 hours. After the mixture was cooled to room temperature, 100 parts of saturated brine and then 700 parts of ion-exchanged water were added, and the mixture was further stirred for 1 hour. Thereafter, the precipitate was obtained by suction filtration and washed with 100 parts of ion exchange water and 100 parts of hexane to obtain 1.93 parts of a compound represented by the formula (1-47).

式（１−４７）で表される化合物の同定；
（元素分析）Ｃ：７０．１ Ｈ：７．７ Ｎ：２．５

Identification of the compound represented by formula (1-47);
(Elemental analysis) C: 70.1 H: 7.7 N: 2.5

式（１−２４）で表される化合物の同定；
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６０３．４
Ｅｘａｃｔ Ｍａｓｓ： ６０２．２ [Synthesis Example 2]
20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under shading conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. did. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 24 parts of a compound represented by the formula (1-24). The yield was 80%.

Identification of the compound represented by formula (1-24);
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−３２）で表される化合物の同定；
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６５９．９
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ [Synthesis Example 3]
A compound represented by the formula (1-32) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of the compound represented by formula (1-32);
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9
Exact Mass: 658.9

[Synthesis Example 4]
A mixture of a compound represented by the formula (A0-1) and a compound represented by the formula (A0-2) (trade name Chugai Aminol Fast Pink R; manufactured by Chugai Kasei Co., Ltd.) 15 Part, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise and 10.9 parts of thionyl chloride was added dropwise while maintaining at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals are separated by filtration, washed thoroughly with ion-exchanged water, dried under reduced pressure at 60 ° C., and compounds represented by xanthene dye 1 (formula (Aa-1-1) to formula (Aa-1-8)) Of 11.3 parts).

[Synthesis Example 5]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Then 46 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A solution is prepared by dissolving in 240 parts of a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) and 185 parts of ethyl lactate, and the resulting solution is added for 4 hours using a dropping funnel. And dropped in a flask kept at 70 ° C.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B1 solution having a solid content of 26%. Resin B1 had a weight average molecular weight of 9.1 × 10 ³ , a molecular weight distribution of 2.1, and a solid content acid value of 120 mg-KOH / g. Resin B1 has the following structural units.

[Synthesis Example 6]
A suitable amount of nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Then 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution prepared by dissolving 225 parts of a mixture of decan-9-yl acrylate (content ratio is 50:50 in molar ratio) and 81 parts of vinyl toluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Was dropped into the flask over 4 hours.
On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at 85 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer solution. This copolymer is referred to as "resin B2." The solid content of the resin B2 solution was 37.5%, and the viscosity measured with a B-type viscometer (23 ° C.) was 246 mPa · s. Resin B2 had a weight average molecular weight of 1.06 × 10 ⁴ , an acid value in terms of solid content of 115 mg-KOH / g, and a molecular weight distribution of 2.01. Resin B2 has the following structural units.

[Synthesis Example 7]
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 7. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate having a tricyclodecane skeleton (dicyclopentanyl methacrylate; FA-513M manufactured by Hitachi Chemical Co., Ltd.) A solution prepared by adding 3.6 g of 2,2′-azobisisobutyronitrile to a mixture of 0 g (0.10 mol) and propylene glycol monomethyl ether acetate 136 g was added dropwise, and stirring was continued at 100 ° C.
Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin B3 solution having a solid content of 29% and a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

The polystyrene-converted weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in the synthesis examples were measured using the GPC method under the following conditions.
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 Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

[Example 1]
<Preparation of colored curable resin composition>
Colorant (A): C.I. I. Pigment Blue 15: 6 (pigment) 22.2 parts Acrylic pigment dispersant 5.6 parts Propylene glycol monomethyl ether acetate 150 parts are mixed and the pigment is sufficiently dispersed using a bead mill.
Colorant (A): Compound represented by formula (1-47) 8.0 parts Resin (B): Resin B1 (in terms of solid content) 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (Kayarad ( (Registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark)) OXE 01; manufactured by BASF) 5 parts Compound (Q): 4-methoxy-1-naphthol (Kinopower (registered trademark) MNT; manufactured by Kawasaki Chemical Co., Ltd.) 10 parts Leveling agent (F): polyether-modified silicone Oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.1 part Solvent (E): Ethyl lactate 603 parts Solvent (E): Propylene glycol 175 parts of coal monomethyl ether acetate was mixed to obtain a colored curable resin composition.

<Preparation of colored pattern>
A colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to obtain a colored composition layer. After standing to cool, the distance between the substrate on which the colored composition layer is formed and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. The colored composition layer after the light irradiation is developed by immersion in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, Post-baking was carried out at 10 ° C. for 10 minutes to obtain a colored pattern.

<Film thickness measurement>
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

<Chromaticity evaluation>
About the obtained coloring pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE using the characteristic function of C light source (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 1.

<Contrast evaluation>
Except not using a photomask at the time of exposure, the same operation as preparation of a colored pattern was performed, and the colored coating film was produced. About the obtained colored coating film, a contrast meter (CT-1; manufactured by Aisaka Electric Co., Ltd., color / color difference meter BM-5A; manufactured by Topcon Co., Ltd., light source: F-10, polarizing film; manufactured by Aisaka Electric Co., Ltd.) The contrast was measured using a blank value of 30000. If the contrast in the colored coating film is high, it can be said that the color pattern has the same high contrast. The results are shown in Table 1.

[Example 2]
Colorant (A): C.I. I. Pigment Blue 15: 6 (pigment) 29.1 parts Acrylic pigment dispersant 11.1 parts Propylene glycol monomethyl ether acetate 194 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
Colorant (A): Compound represented by Formula (1-32) 2.2 parts Resin (B): Resin B2 (solid content conversion) 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (Kayarad ( (Registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark)) OXE 01; manufactured by BASF) 15 parts Compound (Q): 4-methoxy-1-naphthol (Kinopower (registered trademark) MNT; manufactured by Kawasaki Kasei Kogyo Co., Ltd.) 7 parts Leveling agent (F): polyether-modified silicone Oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.33 parts Solvent (E): 4-hydroxy-4-methyl-2-pentanone 03 parts Solvent (E): to obtain a colored curable resin composition by mixing 226 parts of propylene glycol monomethyl ether acetate.

A colored pattern was obtained in the same manner as in Example 1 except that post-baking was performed at 230 ° C. for 30 minutes. The obtained colored pattern was evaluated in the same manner as in Example 1.

[Comparative Example 1]
(A) Colorant: C.I. I. Pigment Blue 15: 6 (pigment) 20 parts Acrylic pigment dispersant 5 parts Propylene glycol monomethyl ether acetate 137 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
(A) Colorant: Xanthene dye 1 3.5 parts (B) Resin: Resin B3 solution 157 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization Initiator: OXE 01 (manufactured by BASF) 15 parts (E) Solvent: 289 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to obtain a colored curable resin composition. About this coloring curable resin composition, operation similar to Example 2 was performed and the coloring pattern was obtained. The obtained colored pattern was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3
A colored curable resin composition is obtained in the same manner as in Example 2 except that the compound represented by the formula (1-32) is replaced with the compound represented by the formula (1-24). A high-contrast color filter is obtained from the colored curable resin composition.

  According to the colored curable resin composition of an Example, it was confirmed that the obtained colored coating film shows high contrast. From this, it can be seen that the colored coating film and the colored pattern obtained from the colored curable resin composition of the present invention are useful as a high-contrast color filter, and the liquid crystal display device including the color filter is excellent in display characteristics. .

  According to the colored curable resin composition of the present invention, a high-contrast color filter can be formed.

21 Glass substrate 22 TFT (switching element)
22a Gate electrode 22b Gate insulating film 22c Polycrystalline silicon film 22d Protective film 23 Color filter layer 23A Colored curable resin composition layer (color filter)
23a Red filter 23b Green filter 23c Blue filter 24 Pixel electrode 27 Signal line 29 Photosensitive resin film (protective film)
201, 202 connection hole

Claims (4)

A colorant, a resin, a polymerizable compound, a polymerization initiator and a compound represented by the formula (Q1),
The colorant is a colorant containing a xanthene dye,
Colored curable resin composition whose content of a coloring agent is 5 to 60 mass% with respect to the total amount of solid content.

[In Formula (Q1), A ¹ and A ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
A ³ , A ⁴ , A ⁵ and A ⁶ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, or A ³ and A ⁴ are carbon atoms to which they are bonded together. A benzene ring may be formed together. ]   The colored curable resin composition according to claim 1, wherein the colorant further comprises a pigment.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 3.

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