JP7312015B2 - Colored curable resin composition - Google Patents

Description

The present invention relates to a colored curable resin composition.

Color filters used in display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays and solid-state imaging devices such as CCD and CMOS sensors are produced from colored curable resin compositions. Such a colored curable resin composition includes a compound represented by the formula (A2-33) and an anthraquinone dye C.I. I. A composition containing Solvent Blue 45 is known (Patent Document 1).

JP 2017-226814 A

The problem to be solved by the present invention is to provide a colored curable resin composition useful for obtaining a color filter having excellent heat resistance when an overcoat is laminated.

［式（Ａ１）中、
Ａ^1a及びＡ^2aは、それぞれ独立に、置換基を有していてもよいフェニレン基を表す。
Ｌ^1a及びＬ^2aは、それぞれ独立に、炭素数１～１２の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＳＯ₂－又は－ＮＲ^11a－に置き換わっていてもよい。
Ｒ^1a～Ｒ^6aは、それぞれ独立に、水素原子、ハロゲン原子又は炭素数１～８のアルキル基を表す。Ｒ^11aは、水素原子、又は炭素数１～８のアルキル基を表す。］
［２］ 前記カルボキシ基を有するキサンテン化合物が式（Ａ２）で表される化合物である［１］に記載の着色硬化性樹脂組成物。

［式（Ａ２）中、
Ｒ^1b～Ｒ^4bは、それぞれ独立に、水素原子、置換基を有していてもよい炭素数６～１０の芳香族炭化水素基、又は置換基を有していてもよい炭素数１～２０の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＣＯ－又は－ＮＲ^11b－で置き換わっていてもよい。Ｒ^1b及びＲ^2bは、一緒になって窒素原子を含む環を形成してもよく、Ｒ^3b及びＲ^4bは、一緒になって窒素原子を含む環を形成してもよい。
Ｒ^6b及びＲ^7b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。
Ｒ^11bは、水素原子、炭素数１～２０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。
ただし、Ｒ^1b～Ｒ^4bのうち少なくとも一つは－ＣＯＯＨを有する炭素数６～１０の芳香族炭化水素基、又は－ＣＯＯＨを有する炭素数１～２０の飽和炭化水素基を表す。］
［３］ 前記着色剤が、さらに青色顔料を含む［１］又は［２］に記載の着色硬化性樹脂組成物。
［４］ ［１］～［３］のいずれかに記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［５］ ［４］に記載のカラーフィルタを含む表示装置。
なお本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組合せて使用することができる。 The present invention is as follows.
[1] containing a coloring agent, a resin, a polymerizable compound and a polymerization initiator,
A colored curable resin composition in which the colorant contains a xanthene compound having a carboxy group and a compound represented by formula (A1).

[In the formula (A1),
A ^1a and A ^2a each independently represent an optionally substituted phenylene group.
L ^1a and L ^2a each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —SO ₂ — or —NR ^11a - may be substituted.
R ^1a to R ^6a each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. R ^11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]
[2] The colored curable resin composition according to [1], wherein the xanthene compound having a carboxyl group is a compound represented by formula (A2).

[In formula (A2),
R ^1b to R ^4b are each independently a hydrogen atom, an optionally substituted C 6-10 aromatic hydrocarbon group, or an optionally substituted C 1-20 and --CH ₂ -- contained in the saturated hydrocarbon group may be replaced with --O--, --CO-- or --NR ^11b --. R ^1b and R ^2b may together form a ring containing a nitrogen atom, and R ^3b and R ^4b may together form a ring containing a nitrogen atom.
R ^6b and R ^7b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
At least one of R ^1b to R ^4b represents an aromatic hydrocarbon group having -COOH and having 6 to 10 carbon atoms or a saturated hydrocarbon group having -COOH and having 1 to 20 carbon atoms. ]
[3] The colored curable resin composition according to [1] or [2], wherein the colorant further contains a blue pigment.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter described in [4].
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.

According to the colored curable resin composition of the present invention, a color filter having excellent heat resistance when an overcoat is laminated can be obtained.

<Colored curable resin composition>
The colored curable resin composition of the present invention includes a coloring agent (hereinafter sometimes referred to as "coloring agent (A)"), a resin (hereinafter sometimes referred to as "resin (B)"), a polymerizable compound (hereinafter sometimes referred to as "resin (B)"), , may be referred to as “polymerizable compound (C)”), and a polymerization initiator (hereinafter, may be referred to as “polymerization initiator (D)”).
In this specification, the compounds exemplified as each component can be used singly or in combination unless otherwise specified.

<Colorant (A)>
The colored curable resin composition of the present invention contains, as the colorant (A), a xanthene compound having a carboxy group and a specific anthraquinone compound described later.

<Xanthene compound>
The number of carboxy groups possessed by the xanthene compound having carboxy groups is, for example, 1-8, preferably 1-4, more preferably 1-2. The xanthene compound preferably has one or more —SO ₃ ^— groups, and when it has —SO ₃ ^— groups, the charge of the compound is preferably neutral. The number of —SO ₃ ^— is preferably 1 to 6, more preferably 1 to 3, and most preferably 1.

As such a xanthene compound having a carboxy group, a rhodamine compound having a carboxy group is preferable, and a compound represented by formula (A2) (hereinafter sometimes referred to as "compound (A2)") is more preferable. Formula (A2) is used to include its tautomer.

［式（Ａ２）中、
Ｒ^1b～Ｒ^4bは、それぞれ独立に、水素原子、置換基を有していてもよい炭素数６～１０の芳香族炭化水素基、又は置換基を有していてもよい炭素数１～２０の飽和炭化水素基を表し、該飽和炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＣＯ－又は－ＮＲ^11b－で置き換わっていてもよい。Ｒ^1b及びＲ^2bは、一緒になって窒素原子を含む環を形成してもよく、Ｒ^3b及びＲ^4bは、一緒になって窒素原子を含む環を形成してもよい。
Ｒ^6b及びＲ^7b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。
Ｒ^11bは、水素原子、炭素数１～２０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。
ただし、Ｒ^1b～Ｒ^4bのうち少なくとも一つは－ＣＯＯＨを有する炭素数６～１０の芳香族炭化水素基、又は－ＣＯＯＨを有する炭素数１～２０の飽和炭化水素基を表す。］

[In formula (A2),
R ^1b to R ^4b are each independently a hydrogen atom, an optionally substituted C 6-10 aromatic hydrocarbon group, or an optionally substituted C 1-20 and --CH ₂ -- contained in the saturated hydrocarbon group may be replaced with --O--, --CO-- or --NR ^11b --. R ^1b and R ^2b may together form a ring containing a nitrogen atom, and R ^3b and R ^4b may together form a ring containing a nitrogen atom.
R ^6b and R ^7b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
At least one of R ^1b to R ^4b represents an aromatic hydrocarbon group having -COOH and having 6 to 10 carbon atoms or a saturated hydrocarbon group having -COOH and having 1 to 20 carbon atoms. ]

Examples of substituents which the aromatic hydrocarbon group or saturated hydrocarbon group represented by R ^1b to R ^4b may have include a halogen atom, —OH, —OR ^21b , —SO ₃ H, and —SO ₃ . ^{-Z +} , -COOH, -COO ^- M ⁺ , -CO ₂ R ^21b , -SR ^21b , -SO ₂ R ^21b , -SO ₃ R ^21b or -SO ₂ NR ^12b R ^13b . R ^21b represents a saturated hydrocarbon group having 1 to 20 carbon atoms. R ^12b and R ^13b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, and R ^12b and R ^13b together represent a nitrogen atom may form a ring containing Z ⁺ is Na ⁺ , K ⁺ , or N ⁺ (R ^15b ) ₄ , M ⁺ is Na ⁺ , K ⁺ , or N ⁺ (R ^16b ) ₄ , and the four R ^15b may be the same or different; and the four R ^16b may be the same or different. R ^15b and R ^16b each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Among the above substituents, -SO ₃ H, -SO ₃ ^{-Z +} , -COOH, -COO ^- M ⁺ and -SO ₂ NR ^12b R ^13b are preferred, and -SO ₃ ^{-Z +} in this case is - _SO3 ^- N ⁺ ( ^R15b ) ₄ is preferred. When R ^1b to R ^4b are aromatic hydrocarbon groups having —COOH, —COO ⁻ M ⁺ etc. as substituents, —COOH and —COO ⁻ M ⁺ are attached to the bonds of the aromatic hydrocarbon groups It is preferably bound at the meta-position or the para-position. When R ^1b to R ^4b are these groups, the colored curable resin composition of the present invention containing the compound (A2) can form a color filter with little generation of foreign matter and excellent heat resistance. When R ^1b to R ^4b are saturated hydrocarbon groups having —COOH, —COO ⁻ M ⁺ etc. as substituents, —COOH and —COO ⁻ M ⁺ are saturated hydrocarbon groups represented by R ^1b to R ^4b It is preferably attached to the terminal carbon atom (primary carbon atom) of the group.

Examples of aromatic hydrocarbon groups having 6 to 10 carbon atoms represented by R ^1b to R ^4b include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group and butylphenyl group.

Examples of saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ^1b to R ^4b , R ^11b to R ^13b and R ^21b include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl. linear alkyl groups such as groups, heptyl groups, octyl groups, nonyl groups, decyl groups, dodecyl groups, hexadecyl groups, and icosyl groups; branched chains such as isopropyl groups, isobutyl groups, isopentyl groups, neopentyl groups, and 2-ethylhexyl groups; cycloalkyl group; alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group. More preferably, the saturated hydrocarbon group has 1 to 10 carbon atoms.

Examples of alkyl groups having 1 to 6 carbon atoms represented by R ^6b , R ^7b , R ^15b and R ^16b include linear groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group. branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group and neopentyl group. However, R ^6b and R ^7b are preferably hydrogen atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R ^11b , R ^12b and R ^13b include benzyl group, phenylethyl group and phenylbutyl group.

a nitrogen atom-containing ring formed by R ^1b and R ^2b together, a nitrogen atom-containing ring formed by R ^3b and R ^4b together, a nitrogen atom formed by R ^12b and R ^13b together Examples of the ring containing include the following. In the formula, * represents a bond.

Examples of N ⁺ (R ^15b ) ₄ and N ⁺ (R ^16b ) ₄ include tetramethylammonium, tetraethylammonium, tetrapropylammonium and tetrabutylammonium.

—OR ^21b includes, for example, alkyloxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy, and the like. is mentioned.
—CO ₂ R ^21b includes, for example, alkyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and icosyloxycarbonyl groups.

—SR ^21b includes, for example, alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and icosylsulfanyl group.
—SO ₂ R ^21b includes, for example, alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and icosylsulfonyl group.
—SO ₃ R ^21b includes, for example, alkyloxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyloxysulfonyl group.

—SO ₂ NR ^12b R ^13b is, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-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 group, 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- N-1 substituted sulfamoyl groups such as (1,5-dimethylhexyl) sulfamoyl group and N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group and N,N-2 substituted sulfamoyl groups such as groups.

The halogen atom as a substituent which the aromatic hydrocarbon group or saturated hydrocarbon group represented by R ^1b to R ^4b may have includes a chlorine atom, a bromine atom and the like.

Compound (A2) preferably satisfies at least one of the requirements (i) to (vi), and at least the requirements of (i), (ii), (iv), and (v) It is more preferable to satisfy one.

(i) R ^1b is a C 1-20 saturated hydrocarbon group containing —COOH, and at least one of R ^2b to R ^4b is an optionally substituted C 6-10 aromatic It is a hydrocarbon group and contains one --COOH in one molecule.
(ii) R ^1b and R ^3b are C 6-10 aromatic hydrocarbon groups containing --COOH;
(iii) R ^1b is a C 6-10 aromatic hydrocarbon group containing --COOH, and R ^3b is a C 1-20 saturated hydrocarbon group containing --COOH.
(iv) R ^2b is a C 3-20 saturated hydrocarbon group containing --COOH, and R ^4b is a C 1-20 saturated hydrocarbon group containing --COOH.
(v) R ^1b is an optionally substituted C 1-20 saturated hydrocarbon group, and R ^2b is a C 6-10 aromatic hydrocarbon group having —COOH.
(vi) R ^1b and R ^2b are a hydrogen atom or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^3b and R ^4b is —COOH; It is an aromatic hydrocarbon group having 6 to 10 carbon atoms.

In requirement (i), R ^1b is a C 1-20 saturated hydrocarbon group having —COOH (preferably a C 1-10 saturated hydrocarbon group), and at least two of R ^2b to R ^4b are , is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. Further, R ^1b is a saturated hydrocarbon group having —COOH and having 1 to 20 carbon atoms (preferably a saturated hydrocarbon group having 1 to 10 carbon atoms), and R ^2b and R ^3b each have a substituent. It is more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be

In requirement (ii), R ^2b and R ^4b are preferably a hydrogen atom or an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, which may have a substituent. A saturated hydrocarbon group having 1 to 20 carbon atoms is more preferable.

In requirement (iv), R ^1b and R ^3b are preferably an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. Further, R ^4b is preferably a saturated hydrocarbon group having 3 to 20 carbon atoms having —COOH, and R ^2b and R ^4b are saturated hydrocarbon groups having 3 to 10 carbon atoms having —COOH. is more preferred.

Further, in requirement (v), R ^3b is an optionally substituted C 1-20 saturated hydrocarbon group, and R ^4b is a C 6-10 aromatic hydrocarbon having —COOH It is preferably a group.

As the compound (A2), a compound represented by formula (A2a) (hereinafter sometimes referred to as "compound (A2a)") is more preferred. Formula (A2a) is used to include its tautomer.

[In the formula (A2a),
R ^31b and R ^32b each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atoms contained in the saturated hydrocarbon groups of R ^31b and R ^32b are —COOH or halogen --CH ₂ -- contained in the saturated hydrocarbon groups of R ^31b and R ^32b may be substituted with --O--, --CO-- or --NR ^11b --.
R ^33b and R ^34b each independently represent -COOH, an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms.
R ^31b and R ^33b may together form a ring containing a nitrogen atom, and R ^32b and R ^34b may together form a ring containing a nitrogen atom.
p and q independently represent an integer of 0 to 5; When p is 2 or more, multiple R ^33b may be the same or different, and when q is 2 or more, multiple R ^34b may be the same or different.
R ^11b has the same meaning as above.
However, the compound represented by formula (A2a) satisfies at least one of the requirements (ia) and (iia).
(ia) one or both of R ^31b and R ^32b is a C 1-10 saturated hydrocarbon group containing —COOH;
(iia) (requirement a) p is 1 or more and at least one of R ^33b is -COOH, (requirement b) q is 1 or more and at least one of R ^34b is -COOH, requirement Satisfies both a and requirement b. ]

Compounds (A2a) include compounds represented by formulas (A2-1) to (A2-52).

The amount of the xanthene compound having a carboxy group is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, for example, 50% by mass, relative to the total amount of the colorant (A). Below, preferably 40% by mass or less, more preferably 30% by mass or less.

<Anthraquinone compound>
The anthraquinone compound used as the colorant (A) is a compound represented by formula (A1) (hereinafter sometimes referred to as "anthraquinone compound (A1)").

［式（Ａ１）中、
Ａ^1a及びＡ^2aは、それぞれ独立に、置換基を有していてもよいフェニレン基を表す。
Ｌ^1a及びＬ^2aは、それぞれ独立に、炭素数１～１２の２価の炭化水素基を表し、該炭化水素基に含まれる－ＣＨ₂－は、－Ｏ－、－ＳＯ₂－又は－ＮＲ^11a－に置き換わっていてもよい。
Ｒ^1a～Ｒ^6aは、それぞれ独立に、水素原子、ハロゲン原子又は炭素数１～８のアルキル基を表す。Ｒ^11aは、水素原子、又は炭素数１～８のアルキル基を表す。］

[In the formula (A1),
A ^1a and A ^2a each independently represent an optionally substituted phenylene group.
L ^1a and L ^2a each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —SO ₂ — or —NR ^11a - may be substituted.
R ^1a to R ^6a each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. R ^11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

Substituents which the phenylene groups represented by A ^1a and A ^2a may have include halogen atoms (chlorine atom, bromine atom, etc.), —R ^21a , —OH, —OR ^21a , —SO ₃ H, -SO ₃ ^- G ⁺ , -COOH, -COO ^- T ⁺ , -CO ₂ R ^21a , -SR ^21a , -SO ₂ R ^21a , -SO ₃ R ^21a or -SO ₂ NR ^12a R ^13a . R ^21a represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and in the case of —R ^21a , R ^21a is preferably an alkyl group having 1 to 8 carbon atoms. R ^12a and R ^13a each independently represent a hydrogen atom, a ^saturated hydrocarbon group having 1 to 20 carbon atoms or ^an aralkyl group having 7 to 10 carbon atoms; may form a ring containing G ⁺ is Na ⁺ , K ⁺ , ^or N ⁺ (R ^15a ) ₄ ; T ⁺ is Na ⁺ , K ⁺ , or N ⁺ (R ^16a ) ₄ ; and the four R ^16a may be the same or different. R ^15a and R ^16a each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Among the above substituents, -R ^21a , -SO ₃ H, -SO ₃ ^- G ⁺ , -COOH, -COO ^- T ⁺ and -SO ₂ NR ^12a R ^13a are preferred, and -SO ₃ ^- G ⁺ -SO ₃ ^- N ⁺ (R ^15a ) ₄ is preferable as the group. The most preferred substituent is ^-R21a .

Examples of alkyl groups having 1 to 8 carbon atoms represented by R ^1a to R ^6a , R ^11a , R ^15a , R ^16a and R ^21a include methyl group, ethyl group, propyl group, butyl group, pentyl group, straight-chain alkyl groups such as hexyl; branched-chain alkyl groups such as isopropyl, isobutyl, isopentyl, and neopentyl. However, R ^1a to R ^6a and R ^11a are preferably hydrogen atoms.

Hydrocarbons having 1 to 12 carbon atoms which are represented by L ^1a and L ^2a and serve as divalent groups include aliphatic saturated hydrocarbons having 1 to 12 carbon atoms, benzene, and alkyl groups having 1 to 8 carbon atoms. and benzene. Examples of the divalent aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms include methylene group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane- Linear alkanediyl groups having bonds at both ends such as 1,5-diyl group and hexane-1,6-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane- 1,2-diyl group, propane-2,2-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, 2-methylpropane-1,1-diyl group, 2-methylpropane-1,2-diyl group, 2-methylpropane-1,3-diyl group, 2-methyl Propane-1,4-diyl group, 2-methylpropane-2,3-diyl group, 2-methylpropane-2,4-diyl group, 2-methylpropane-3,3-diyl group, 2-methylpropane- A 3,4-diyl group, a 2-methylpropane-4,4-diyl group and the like can be mentioned, and a linear alkanediyl group having bonds at both ends is preferred.

Examples of benzene having an alkyl group having 1 to 8 carbon atoms include methylbenzene, dimethylbenzene, ethylbenzene, propylbenzene, ethyl(methyl)benzene, butylbenzene, ethyl(dimethyl)benzene and the like, and the benzene having 1 to 8 carbon atoms. The divalent group formed by benzene having an alkyl group of may be an aspect having two bonds in the alkyl group, an aspect having two bonds in the benzene ring, or one bond in the alkyl group and one bond on the benzene ring. An aspect in which the alkyl group has one bond and the benzene ring has one bond is preferred.

Examples of saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ^12a , R ^13a and R ^21a include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; branched chain alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group. More preferably, the saturated hydrocarbon group has 1 to 10 carbon atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms represented by R ^12a and R ^13a include benzyl group, phenylethyl group and phenylbutyl group.

Examples of the nitrogen atom-containing ring formed by R ^12b and R ^13b together include the following. In the formula, * represents a bond.

Examples of N ⁺ (R ^15a ) ₄ and N ⁺ (R ^16a ) ₄ include tetramethylammonium, tetraethylammonium, tetrapropylammonium and tetrabutylammonium.

—OR ^21a includes, for example, alkyloxy groups such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy. is mentioned.
—CO ₂ R ^21a includes, for example, alkyloxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and icosyloxycarbonyl groups.

—SR ^21a includes, for example, alkylsulfanyl groups such as methylsulfanyl group, ethylsulfanyl group, butylsulfanyl group, hexylsulfanyl group, decylsulfanyl group and icosylsulfanyl group.
—SO ₂ R ^21a includes, for example, alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and icosylsulfonyl group.
—SO ₃ R ^21a includes, for example, alkyloxysulfonyl groups such as methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and icosyloxysulfonyl groups.

—SO ₂ NR ^12a R ^13a is, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-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 group, 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- N-1 substituted sulfamoyl groups such as (1,5-dimethylhexyl) sulfamoyl group and N-(1,1,2,2-tetramethylbutyl) sulfamoyl group;
N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group moyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, N,N-heptylmethylsulfamoyl group and N,N-2 substituted sulfamoyl groups such as groups.

The halogen atom represented by R ^1a to R ^6a and the halogen atom as a substituent which the phenylene group represented by A ^1a and A ^2a may have include a chlorine atom and a bromine atom.

The anthraquinone compound (A1) includes *-L ^1a -** (* represents a bond with A ^1a and ** represents a bond with CO ₂ H) and *-L ^2a of formula (A1). -** (* represents a bond with A ^2a , ** represents a bond with CO ₂ H) independently of each other, compounds having structures represented by formulas (A1a) to (A1h) is preferred.

［式中、Ｒ^31aは、炭素数が１～１０のアルカンジイル基を表し、Ｒ^32aは炭素数が１～４のアルキル基が結合していてもよいフェニレン基を表し、Ｒ^33aは炭素数が１～４のアルカンジイル基を表す。＊はＡ^1a又はＡ^2aとの結合手を表し、＊＊はＣＯ₂Ｈとの結合手を表す。］
（Ａ１ａ）～（Ａ１ｈ）中、（Ａ１ａ）、（Ａ１ｆ）などが好ましい。

[In the formula, R ^31a represents an alkanediyl group having 1 to 10 carbon atoms, R ^32a represents a phenylene group optionally bonded to an alkyl group having 1 to 4 carbon atoms, and R ^33a represents a represents 1 to 4 alkanediyl groups. * represents a bond with A ^1a or A ^2a , and ** represents a bond with CO ₂ H. ]
Among (A1a) to (A1h), (A1a) and (A1f) are preferred.

Examples of the anthraquinone compound (A1) include compounds represented by the formula (A1X). Specific examples of compounds represented by formula (A1X) are represented by numbers (A1X-1) to (A1X-36) in Table 1.

In Table 1, Me represents a methyl group, and RX1 to RX5 and RY1 to RY4 each represent groups represented by the following formulas. In the formula, * represents a bond.

The amount of the anthraquinone compound (A1) is, for example, 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and for example 50% by mass or less, relative to the total amount of the colorant (A). , preferably 40% by mass or less, more preferably 30% by mass or less.

The amount of the anthraquinone compound (A1) is, for example, 20% by mass or more, preferably 30% by mass or more, more preferably 40% by mass or more, based on the total amount of the xanthene compound having a carboxy group and the anthraquinone compound (A1). and, for example, 80% by mass or less, preferably 70% by mass or less, and more preferably 60% by mass or less.

Anthraquinone compound (A1) can be produced according to a known method. A compound represented by formula (A1X2) can be produced, for example, according to the following synthetic scheme.

(In the formula, A ^1a , A ^2a , R ^1a to R ^6a and R ^31a have the same meanings as above. ^{R 51a} represents an alkyl group having 1 to 4 carbon atoms.)
More specifically, 1,4,9,10-tetrahydroxyanthracene represented by the formula (A1Z) is oxidized and its hydroxyl group is converted to a hydroxylamine compound (specifically, H ₂ N—A ^1a —OH, H _2N --A ^2a --OH) to produce a compound represented by formula ⁽ A1Y), and combining the compound represented by formula ( ^A1Y ₎ with The target compound (A1X2) can be produced by decondensing the compound with HBr to form an ether compound and then hydrolyzing the --CO ₂ R ^51a group.

<Third Colorant>
The colorant (A) may contain a colorant other than the xanthene compound and the anthraquinone compound (A1) having a carboxy group (hereinafter sometimes referred to as "third colorant").
The third colorant may be either dye (AA) or pigment (AB). As the dye (AA), known dyes can be used as long as they do not contain a xanthene compound having a carboxyl group and an anthraquinone compound (A1). Examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Dyes include, for example, compounds classified as having hues other than pigments in the Color Index (published by The Society of Dyers and Colorists), and known dyes described in Dye Note (Shikisensha). be done. Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes (excluding xanthene compounds having a carboxy group), phthalocyanine dyes, anthraquinone dyes (excluding anthraquinone compound (A1)). , naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferred.

Specific examples of dyes include C.I. I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow is omitted and only the number is described.), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 , 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. solvent blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. C.I. I. solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. acid blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. acid green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. acid dye,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. C.I. I. disperse dyes,
C. I. Basic Red 1, 10;
C. I. basic blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. basic violet 2;
C. I. basic red 9;
C. I. Basic Green 1; I. basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive Orange 16;
C. I. C.I. Reactive Red 36; I. reactive dyes,
C. I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. C.I. I. modant dye,
C. I. C.I. I. and vat dyes.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

The xanthene compound having a carboxy group and the anthraquinone compound (A1) are classified as dyes, and the total amount of the xanthene compound having a carboxy group and the anthraquinone compound (A1) in all dyes is, for example, 30% by mass or more, preferably 60%. It is at least 90% by mass, more preferably at least 90% by mass, may be at least 95% by mass, or may be at least 100% by mass.

The pigment (AB) is not particularly limited, and known pigments can be used. Examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colorists).
Examples of pigments 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 Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60;
C. I. Violet color pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23, 25;
C. I. Black pigments such as Pigment Black 1 and 7 are included.

As a pigment, C.I. I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6, 60; C.I. I. Violet color pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 are preferred; I. Pigment Blue 15:3, 15:6 and C.I. I. Pigment Violet 23 is more preferred, C.I. I. Pigment Blue 15:6 is more preferred. Inclusion of the pigment facilitates optimization of the transmission spectrum, and improves the light resistance and chemical resistance of the color filter.

If necessary, the pigment is subjected to rosin treatment, surface treatment using a pigment derivative into which an acidic group or basic group is introduced, graft treatment to the pigment surface with a polymer compound, etc., atomization by a sulfuric acid atomization method, etc. Treatment, washing treatment with an organic solvent, water, or the like for removing impurities, removal treatment by an ion exchange method or the like for ionic impurities, or the like may be performed.
The pigment preferably has a uniform particle size. A pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained by adding the pigment dispersant and performing the dispersion treatment.

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 pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), Ajisper (Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.
When a 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, relative to the total amount of the pigment (AB). When the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a uniformly dispersed pigment dispersion.

As the third coloring agent, the pigment (AB) is preferable, and the blue pigment is more preferable.
The amount of the third colorant is, for example, 0% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 60% by mass or more, relative to the total amount of the colorant (A). and, for example, 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less.

When pigment (AB) is included, the content ratio of all dyes (xanthene compound having a carboxy group, anthraquinone compound (A1), dye (AA)) and pigment (AB) in colorant (A) (all dyes /pigment (AB)) is usually 1/99 to 99/1, preferably 10/90 to 60/40, and more preferably 15/85 to 30/70 on a mass basis.

The content of the coloring agent (A) in the colored curable resin composition is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, more preferably 8 to 55% by mass, based on the total solid content. 10 to 50% by mass. When the content of the coloring agent (A) is within the above range, the color density of the color filter is sufficient, and the necessary amount of resin and polymerizable compound can be contained in the composition. A pattern with sufficient physical strength can be formed. Here, the "total amount of solid content" in this specification refers to the amount obtained by subtracting 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.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and contains at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter " A resin having a structural unit derived from a monomer (a) is more preferable. The resin (B) is further derived from a monomer (b) having a cyclic ether structure with 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b)"). Structural unit, monomer (a) and copolymerizable monomer (c) (but different from monomer (a) and monomer (b)) (hereinafter “monomer (c) ) and structural units having an ethylenically unsaturated bond in the side chain.

Specific examples of the monomer (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, monosuccinic acid [2 -(meth)acryloyloxyethyl] and the like, preferably acrylic acid, methacrylic acid, and maleic anhydride.

Monomer (b) is a monomer having a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and a (meth)acryloyloxy group. body is preferred.
In this 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 the monomer (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)
acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane, tetrahydrofurfuryl (meth)acrylate and the like, preferably glycidyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1 .0 ^2,6 ]decyl (meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane.

Examples of the monomer (c) include methyl (meth)acrylate, butyl (meth)acrylate cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ] (meth)acrylates such as decan-8-yl (meth)acrylate, benzyl (meth)acrylate and 2-hydroxyethyl (meth)acrylate; maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide; Examples thereof include styrene-based monomers such as styrene and vinyltoluene, and preferred are styrene, vinyltoluene, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and the like.
The (meth)acrylates, maleimides, styrenic monomers, etc. may be combined as appropriate, and a combination of (meth)acrylates and maleimides is preferred.

The structural unit having an ethylenically unsaturated bond in the side chain is obtained by adding the monomer (b) to the copolymer structure of the monomer (a) and the monomer (c), or by adding the monomer (b) and the monomer (a) is added to the copolymer structure of the monomer (c), or the monomer (a) is added to the copolymer structure of the monomer (b) and the monomer (c). It can be constructed by addition and further reaction with a carboxylic acid anhydride.

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 still more preferably 5,000 to 30,000. .
The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

The acid value of the resin (B) is preferably 20 to 170 mg-KOH/g, more preferably 30 to 150 mg-KOH/g, still more preferably 40 to 135 mg-KOH/g, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example. .

The content of the resin (B) is preferably 5 to 70% by mass, more preferably 15 to 60% by mass, and still more preferably 20% by mass, relative to the total solid content of the colored curable resin composition. ~50% by mass.

<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). is a (meth)acrylic acid ester compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more 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 and the like.

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

The content of the polymerizable compound (C) is preferably 5 to 65% by mass, more preferably 15 to 60% by mass, and still more preferably the total solid content of the colored curable resin composition. is 20 to 50% by mass.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating active radicals, acids, etc. by the action of light or heat, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl ) octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenyl sulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4- morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole and the like.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, with respect to 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 tends to be increased and the exposure time tends to be shortened, thereby improving the productivity of the color filter.

<Polymerization initiation aid (D1)>
The colored curable resin composition of the present invention may contain a polymerization initiation aid (D1). The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator.
Examples of the polymerization initiation aid (D1) include 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-phenylglycine and the like.

When using these polymerization initiation aids (D1), the content 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). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of color filters tends to improve.

<Solvent (E)>
The colored curable resin composition preferably contains a solvent (E). The solvent (E) is not particularly limited, and solvents commonly used in the field can be used. For example, ester solvent (solvent containing -COO- in the molecule but not containing -O-), ether solvent (solvent containing -O- in the molecule but not containing -COO-), ether ester solvent (solvent containing -COO- in the molecule 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-, - solvents containing no CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As a solvent,
Ester solvents (-COO- solvent containing and not containing -O-);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether (solvents containing -O- in the molecule but not containing -COO- );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (-COO- and a solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone, cyclohexanone (solvents containing -CO- in the molecule but not containing -COO-) ;
Alcohol solvents such as butanol, cyclohexanol, propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-);
amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone;
More preferred solvents are propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate and ethyl 3-ethoxypropionate.

When the solvent (E) is included, the content of the solvent (E) is preferably 60 to 95% by mass, more preferably 65 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. is. In other words, the total solid content of the colored curable resin composition is preferably 5 to 40% by mass, more preferably 8 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is improved, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be improved. .

<Leveling agent (F)>
The colored curable resin composition may contain a leveling agent (F). Examples of the leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain.

Examples of silicone-based surfactants include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray SH7PA, Toray DC11PA, Toray SH21PA, Toray SH28PA, Toray SH29PA, Toray SH30PA, Toray SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.); KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) mentioned.

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

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

When the leveling agent (F) is included, the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.001 to 0.2% by mass, based on the total amount of the colored curable resin composition. 002 to 0.1% by mass. This content does not include the content of the pigment dispersant. 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 optionally contains additives known in the art such as fillers, polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like. It's okay.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention comprises a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an optional polymerization initiation aid (D1). , solvent (E), leveling agent (F) and other ingredients.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred.

Since the colored curable resin composition contains a xanthene compound having a carboxy group and an anthraquinone compound (A1), the color filter produced from this colored curable resin composition has heat resistance when an overcoat is laminated. will be superior. The color filter is useful as a color filter for use in display devices (eg, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples. In the examples, percentages and parts representing contents or usage amounts are based on mass unless otherwise specified.

In the following examples, the structures of the compounds were confirmed by mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Model LC/MSD manufactured by Agilent).

[Synthesis Example 1]

66.9 parts of chlorosulfuric acid was added to a flask equipped with a cooling tube and a stirrer, cooled to 10°C or less, and C.I. I. 3.6 parts of Solvent Blue 104 (Compound (A1Y-1)) were slowly added. After that, the reaction solution was allowed to take its own course, and the temperature was raised to room temperature (25° C.), and the mixture was stirred at the same temperature for 6 hours. The resulting reaction solution was added dropwise to 108 parts of ice water to form a suspension, and the precipitated crystals were separated by filtration, washed thoroughly with ion-exchanged water, dried under reduced pressure at 60° C. overnight, and represented by the formula (A1Y-2). 4.9 parts of the crude compound represented were obtained. This was purified by silica gel column chromatography (solvent: chloroform) to obtain 3.4 parts of the compound represented by formula (A1Y-2).

In a flask equipped with a cooling tube and a stirring device, 4.6 parts of methyl 3-amino-4-methylbenzoate and 16.5 parts of chloroform are added and cooled to 10 ° C. or less, and the formula (A1Y-2) is stirred. A solution prepared by dissolving 2.4 parts of the compound represented by in 16.5 parts of chloroform, and 2.2 parts of pyridine were added dropwise thereto. After that, the reaction solution was allowed to take its own course, and the temperature was raised to room temperature, and the mixture was stirred at the same temperature for 5.5 hours. 150 parts of chloroform and 50 parts of 2N hydrochloric acid were added to the resulting reaction solution to separate the layers, and the organic layer was washed twice with 50 parts of 2N hydrochloric acid. The resulting organic layer was dried over excess sodium sulfate, and chloroform was distilled off from the solution obtained after filtration under reduced pressure to obtain 3.4 parts of the crude compound represented by the formula (A1Y-3). . This was purified by silica gel column chromatography (solvent: chloroform) to obtain 2.8 parts of the compound represented by formula (A1Y-3).

Identification of compound represented by formula (A1Y-3) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 929.2
Exact Mass: 928.3

2.5 parts of the compound represented by the formula (A1Y-3), 35 parts of N-methylpyrrolidone and 17 parts of an 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer and stirred at 50°C for 5 hours. Stirred for an hour. After allowing to cool, the resulting reaction solution was added to 175 parts of 2N hydrochloric acid to form a suspension, and the precipitated crystals were filtered off, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60°C overnight to obtain the formula ( 2.1 parts of the compound represented by A1X-36) were obtained.

Identification of compound represented by formula (A1X-36) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 901.2
Exact Mass: 900.3

[Synthesis Example 2]

5 parts of the compound represented by formula (A1Z), 35 parts of 1-butanol, 5.1 parts of boric acid, and 11.3 parts of 4-amino-3,5-xylenol are added to a flask equipped with a condenser and a stirrer. was added and stirred at 115° C. for 34 hours. After allowing to cool, the obtained reaction solution was added to 15 parts of 6N hydrochloric acid to form a suspension, and the precipitated crystals were separated by filtration and thoroughly washed with deionized water to obtain 24.8 parts of wet crystals. This was added to 124 parts of 2N hydrochloric acid to form a suspension, and after stirring at room temperature, the crystals were separated by filtration and thoroughly washed with deionized water to obtain 7.4 parts of wet crystals. This was added to 74 parts of chloroform to form a suspension, and after stirring at room temperature, the crystals were separated by filtration, washed with chloroform and dried under reduced pressure at 60° C. overnight to obtain a crystal represented by the formula (A1Y-4). 5.8 parts of crude compound was obtained. 5.8 parts of the crude compound represented by formula (A1Y-4) was added to 58 parts of 2-methylpyrrolidone, and the mixture was stirred at 70° C. for 4 hours. After allowing to cool, the obtained reaction solution was added to 579 parts of 2N hydrochloric acid to form a suspension, and the precipitated crystals were separated by filtration and thoroughly washed with deionized water to obtain 16.9 parts of wet crystals. This was added to 58 parts of chloroform to form a suspension, and after stirring at room temperature for 3 hours, the crystals were separated by filtration, washed with chloroform, and dried under reduced pressure at 60° C. overnight to obtain the compound of formula (A1Y-4). 5.5 parts of the indicated compound are obtained.

Identification of compound represented by formula (A1Y-4) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 479.5
Exact Mass: 478.2

5 parts of the compound represented by the formula (A1Y-4), 35 parts of N-methylpyrrolidone, 5.8 parts of potassium carbonate, and 12.2 parts of ethyl 4-bromobutyrate are placed in a flask equipped with a condenser and a stirrer. and stirred at 115° C. for 7.5 hours. After allowing to cool, 70.2 parts of N-methylpyrrolidone and 65.8 parts of 8% aqueous sodium hydroxide solution were added to the resulting reaction solution, and the mixture was stirred at 100° C. for 3.5 hours. After standing to cool, the obtained reaction solution was added to 1000 parts of 2N hydrochloric acid to form a suspension, and after stirring at room temperature, the crystals were separated by filtration, washed thoroughly with ion-exchanged water, and 26.5 parts of wet crystals. got This is added to 265 parts of ion-exchanged water to form a suspension, stirred at room temperature, the crystals are separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60° C. overnight to give the formula (A1X-12). ) to obtain 6.0 parts of a crude compound represented by the following formula. 12 parts of methanol was added to 3.9 parts of the crude compound represented by the formula (A1X-12) to form a suspension, which was stirred at room temperature for 1 hour, and the crystals were separated by filtration and washed with methanol. , and dried under reduced pressure at 60°C overnight to obtain 3.4 parts of the compound represented by the formula (A1X-12).

Identification of compound represented by formula (A1X-12) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M + H] ⁺ 651.5
Exact Mass: 650.3

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirrer, 3 parts of Pink Base represented by the formula (A2Y-1) (manufactured by Chugai Kasei Co., Ltd.), 21 parts of N-methylpyrrolidone and 1.3 parts of potassium hydroxide were added. After adding and stirring at room temperature for 1 hour, 2.3 parts of ethyl acrylate was added and the mixture was stirred at the same temperature for 2 hours. When the resulting reaction solution was added to 105 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 3.5 parts of the compound represented by the formula (A2Y-2).

Identification of compound represented by formula (A2Y-2) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 675.3
Exact Mass: 674.3

1 part of the compound represented by the formula (A2Y-2), 7 parts of methanol and 3.0 parts of an 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer, and stirred at room temperature for 9.5 hours. . When the resulting reaction solution was added to 35 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 0.9 parts of the compound represented by formula (A2-1).

Identification of compound represented by formula (A2-1) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 647.5
Exact Mass: 646.2

[Synthesis Example 4]
In a flask equipped with a condenser and a stirrer, 1 part of Pink Base represented by the formula (A2Y-1) (manufactured by Chugai Kasei Co., Ltd.), 7 parts of N-methylpyrrolidone, 1.0 parts of potassium carbonate and 4 -2.0 parts of ethyl bromobutyrate was added and stirred at 100°C for 7.5 hours. After allowing to cool, 20 parts of 2N hydrochloric acid was added to the resulting reaction solution, and the mixture was extracted twice with 45 parts of chloroform. The chloroform layers were combined, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was dried under reduced pressure at 60° C. to obtain 4.1 parts of crude compound represented by formula (A2Y-3).

Identification of compound represented by formula (A2Y-3) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 803.5
Exact Mass: 802.3

4.1 parts of the compound represented by the formula (A2Y-3), 9.8 parts of methanol and 3.5 parts of an 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer and stirred at room temperature for 6 hours. Stirred for an hour. When the resulting reaction solution was added to 30 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 1.0 parts of the compound represented by the formula (A2-33).

Identification of compound represented by formula (A2-33) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 747.5
Exact Mass: 746.3

[Synthesis Example 5]
In a flask equipped with a cooling tube and a stirrer, 3 parts of Pink Base represented by the formula (A2Y-1) (manufactured by Chugai Kasei Co., Ltd.), 21 parts of N-methylpyrrolidone and 1.7 parts of t-butoxy potassium was added and stirred at room temperature for 30 minutes, 1.6 parts of 1-bromopropane was added and stirred at the same temperature for 1 hour. The resulting reaction solution was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 1 hour to precipitate crystals. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 3.0 parts of the compound represented by the formula (A2Y-4).

Identification of compound represented by formula (A2Y-4) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 617.5
Exact Mass: 616.2

1 part of the compound represented by formula (A2Y-4), 7 parts of N-methylpyrrolidone, 0.5 parts of potassium carbonate and 1.0 parts of ethyl 4-bromobutyrate were added to a flask equipped with a condenser and a stirrer. The mixture was stirred at 100° C. for 5.5 hours. When the resulting reaction solution was added to 35 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 1.2 parts of the compound represented by the formula (A2Y-5).

Identification of compound represented by formula (A2Y-5) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 731.5
Exact Mass: 730.3

1 part of the compound represented by the formula (A2Y-5), 7 parts of methanol and 2.7 parts of 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer, and stirred at room temperature for 3.5 hours. . When the resulting reaction solution was added to 21 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 0.9 parts of the compound represented by the formula (A2-8).

Identification of compound represented by formula (A2-8) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 703.5
Exact Mass: 702.3

[Synthesis Example 6]
In a flask equipped with a condenser and a stirrer, 0.5 parts of the compound represented by the formula (A2Y-2), 3.5 parts of N-methylpyrrolidone, 0.26 parts of potassium carbonate and 2.3 parts of 1-bromopropane was added and stirred at room temperature for 80 hours. When the resulting reaction solution was added to 70 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 0.5 part of the compound represented by the formula (A2Y-6).

Identification of compound represented by formula (A2Y-6) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 717.5
Exact Mass: 716.3

0.5 parts of the compound represented by the formula (A2Y-6), 3.4 parts of methanol and 1.3 parts of 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer and stirred at room temperature for 2 hours. Stirred for an hour. When the resulting reaction solution was added to 70 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 0.4 parts of the compound represented by the formula (A2-4).

Identification of compound represented by formula (A2-4) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 689.5
Exact Mass: 688.3

[Synthesis Example 7]
1.5 parts of Pink Base represented by the formula (A2Y-1) (manufactured by Chugai Kasei Co., Ltd.), 10.5 parts of N-methylpyrrolidone, and 1.5 parts of potassium carbonate were placed in a flask equipped with a cooling tube and a stirrer. 1 part and 0.5 part of ethyl 4-bromobutyrate were added and stirred at 90° C. for 4.5 hours. When the resulting reaction solution was added to 52.5 parts of ion-exchanged water and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with deionized water, and dried at 60° C. under reduced pressure. The resulting crude product was purified by silica gel column chromatography (mobile phase: chloroform/methanol-10/1) to obtain 0.2 parts of the compound represented by formula (A2Y-7).

Identification of compound represented by formula (A2Y-7) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 689.5
Exact Mass: 688.3

0.2 parts of the compound represented by the formula (A2Y-7), 1.6 parts of methanol and 1.0 parts of 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer and stirred at room temperature for 2 hours. Stirred for half an hour. When the resulting reaction solution was added to 16 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 0.2 parts of the compound represented by the formula (A2-5).

Identification of compound represented by formula (A2-5) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 661.5
Exact Mass: 660.3

[Synthesis Example 8]

In a flask equipped with a condenser and a stirrer, 5 parts of 3,6-dichlorosulfofluorescein represented by the formula (A2Y-8) (manufactured by Chugai Kasei Co., Ltd.), 35 parts of N-methylpyrrolidone and 3-amino 12.2 parts of methyl-4-methylbenzoate was added and stirred at 130° C. for 7 hours. After standing to cool, the obtained reaction solution was added to an aqueous solution of 7.5 parts of concentrated hydrochloric acid and 70 parts of ion-exchanged water, and the mixture was stirred at room temperature for 30 minutes to precipitate crystals. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 6.6 parts of the compound represented by the formula (A2Y-9).

Identification of compound represented by formula (A2Y-9) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 663.5
Exact Mass: 662.2

6 parts of the compound represented by the formula (A2Y-9), 42 parts of N-methylpyrrolidone, 5.0 parts of potassium carbonate and 6.6 parts of 1-bromopropane are added to a flask equipped with a condenser and a stirrer. The mixture was stirred at 90° C. for 6 hours. After standing to cool, the resulting reaction solution was added to 210 parts of ion-exchanged water and stirred at room temperature for 30 minutes to precipitate crystals. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 5.9 parts of the compound represented by the formula (A2Y-10).

Identification of compound represented by formula (A2Y-10) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 747.8
Exact Mass: 746.3

3 parts of the compound represented by formula (A2Y-10), 21 parts of methanol and 8.0 parts of 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer, and stirred at room temperature for 8 hours. When the resulting reaction solution was added to 105 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 2.5 parts of the compound represented by the formula (A2-44).

Identification of compound represented by formula (A2-44) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 719.5
Exact Mass: 718.2

[Synthesis Example 9]
In a flask equipped with a condenser and a stirrer, 5 parts of 3,6-dichlorosulfofluorescein (manufactured by Chugai Kasei Co., Ltd.) represented by the formula (A2Y-8), 35 parts of N-methylpyrrolidone and 4- 12.2 parts of methyl amino-3-methylbenzoate was added and stirred at 130° C. for 16 hours. After standing to cool, the obtained reaction solution was added to an aqueous solution of 7.5 parts of concentrated hydrochloric acid and 70 parts of ion-exchanged water, and the mixture was stirred at room temperature for 30 minutes to precipitate crystals. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 6.5 parts of the compound represented by the formula (A2Y-11).

Identification of compound represented by formula (A2Y-11) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 663.8
Exact Mass: 662.2

6 parts of the compound represented by the formula (A2Y-11), 42 parts of N-methylpyrrolidone, 5.0 parts of potassium carbonate and 6.6 parts of 1-bromopropane are added to a flask equipped with a condenser and a stirrer. The mixture was stirred at 90° C. for 8 hours. After standing to cool, the resulting reaction solution was added to 210 parts of ion-exchanged water and stirred at room temperature for 30 minutes to precipitate crystals. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 6.0 parts of the compound represented by the formula (A2Y-12).

Identification of compound represented by formula (A2Y-12) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 747.8
Exact Mass: 746.3

3 parts of the compound represented by the formula (A2Y-12), 21 parts of methanol and 8.0 parts of an 8% aqueous sodium hydroxide solution were added to a flask equipped with a condenser and a stirrer and stirred at room temperature for 8.5 hours. . When the resulting reaction solution was added to 105 parts of 2N hydrochloric acid and stirred at room temperature for 30 minutes, crystals precipitated. Precipitated crystals were separated by filtration, thoroughly washed with ion-exchanged water, and dried at 60° C. under reduced pressure to obtain 2.0 parts of the compound represented by the formula (A2-48).

Identification of compound represented by formula (A2-48) (mass spectrometry) ionization mode = ESI ⁺ : m/z = [M+H] ⁺ 719.5
Exact Mass: 718.2

[Synthesis Example 10]
A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen. Then, 38 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 of 25 parts of a mixture of decane-9-yl acrylate (content ratio is 1:1 in molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate. It was added dropwise over 5 hours. On the other hand, a solution of 5 parts of 2,2-azobisisobutyronitrile dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of dropping, the solution was held at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution having a viscosity of 23 mPas as measured by a Brookfield viscometer (23°C) and a solid content of 25.6%. rice field. The resulting copolymer had a weight average molecular weight Mw of 8.0×10 ³ , a dispersity of 2.1, and an acid value converted to solid content of 109 mg-KOH/g. Resin B1 has the following structural units.

[Example 1]
(Preparation of colored curable resin composition 1)
(A) Colorant: C.I. I. Pigment Blue 15:6 (pigment) 29 parts Acrylic pigment dispersant 10.2 parts Propylene glycol monomethyl ether acetate 241 parts were mixed, and the pigment was sufficiently dispersed using a bead mill. Then,
(A) Colorant: 3.6 parts of the compound represented by the formula (A2-33) (A) Colorant: 3.6 parts of the compound represented by the formula (A1X-36) (B) Resin: Resin B1 ( Solid content conversion) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-Phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 8 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.15 parts (E) Solvent: 4-hydroxy-4-methyl-2-pentanone 51 parts (E) Solvent: propylene glycol monomethyl ether acetate 413 parts are mixed to form a colored curable resin composition got 1.

[Example 2]
A colored curable resin composition 2 was obtained in the same manner as in Example 1, except that the compound represented by the formula (A1X-36) was replaced with the compound represented by the formula (A1X-12).

[Example 3]
A colored curable resin composition 3 was obtained in the same manner as in Example 1, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-44).

[Example 4]
A colored curable resin composition 4 was obtained in the same manner as in Example 1, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-48).

[Example 5]
A colored curable resin composition 5 was obtained in the same manner as in Example 1, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-1).

[Example 6]
A colored curable resin composition 6 was obtained in the same manner as in Example 1, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-8).

[Example 7]
A colored curable resin composition 7 was obtained in the same manner as in Example 1, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-4).

[Example 8]
A colored curable resin composition 8 was obtained in the same manner as in Example 1, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-5).

[Comparative Example 1]
The compound represented by the formula (A1X-36) was prepared by C.I. I. A colored curable resin composition was obtained in the same manner as in Example 1 except that Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant) was used.

<Preparation of color filter (coloring pattern)>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating, and then prebaked at 100° C. for 3 minutes to obtain a colored curable resin composition layer. After cooling, the distance between the substrate on which the colored curable resin composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere. Light irradiation was performed at an exposure dose of 150 mJ/cm ² (365 nm standard). A photomask having a 100 μm line-and-space pattern was used. The colored composition layer after light irradiation is developed by immersion in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24 ° C. for 60 seconds, washed with water, and heated at 230 in an oven. C. for 20 minutes to obtain a color filter.

<Film thickness measurement>
The film thickness of the resulting color filter was measured using a film thickness measuring device (DEKTAK3; manufactured by Japan Vacuum Engineering Co., Ltd.). Table 2 shows the results of Examples 1 to 8 and Comparative Example 1.

<Preparation of curable composition for overcoat>
Styrene/methacrylic acid/glycidyl methacrylate copolymer (mass ratio: 30/20/50; synthesized by the method described in JP-A-11-133600; molecular weight: 21,000) 60 parts, dipentaerythritol hexaacrylate (Kayarad (registered trademark) PHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF) ) and 197 parts of diethylene glycol dimethyl ether were mixed to prepare a curable composition for overcoat.

<Heat resistance evaluation of laminated film>
On the resulting color filter, the curable composition for overcoat was applied by a spin coating method so that the film thickness after drying was 1.5 μm, and then in a clean oven at 100° C. for 3 minutes. A laminated film was created by pre-baking and post-baking at 230° C. for 20 minutes. The laminated film is heated at 250 ° C. for 2 hours in a clean oven, and the xy chromaticity coordinates (x, y) before and after heating and the Y measurement value are calculated according to the method described in JIS Z 8730: 2009 (7. Color difference calculation method). to calculate the color difference ΔE*ab. Table 2 shows the results of Examples 1 to 8 and Comparative Example 1. A smaller ΔE*ab means a smaller color change.

[Example 9]
(Preparation of colored curable resin composition 9)
(A) Colorant: C.I. I. Pigment Blue 15:6 (pigment) 31 parts Acrylic pigment dispersant 10.9 parts Propylene glycol monomethyl ether acetate 257 parts were mixed, and the pigment was sufficiently dispersed using a bead mill. Then,
(A) Colorant: 3.7 parts of the compound represented by the formula (A2-33) (A) Colorant: 1.8 parts of the compound represented by the formula (A1X-36) (B) Resin: Resin B1 ( Solid content conversion) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-Phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 8 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: Toray Dow Corning Co., Ltd.) 0.16 parts (E) Solvent: 4-hydroxy-4-methyl-2-pentanone 57 parts (E) Solvent: Propylene glycol monomethyl ether acetate 382 parts mixed to color curable resin composition got 9.

[Example 10]
A colored curable resin composition 10 was obtained in the same manner as in Example 9, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-44).

[Example 11]
A colored curable resin composition 11 was obtained in the same manner as in Example 9, except that the compound represented by the formula (A2-33) was replaced with the compound represented by the formula (A2-48).

[Example 12]
A colored curable resin composition 12 was obtained in the same manner as in Example 9, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-1).

[Example 13]
A colored curable resin composition 13 was obtained in the same manner as in Example 9, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-8).

[Example 14]
A colored curable resin composition 14 was obtained in the same manner as in Example 9, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-4).

[Example 15]
A colored curable resin composition 15 was obtained in the same manner as in Example 9, except that the compound represented by formula (A2-33) was replaced with the compound represented by formula (A2-5).

[Comparative Example 2]
The compound represented by the formula (A1X-36) was prepared by C.I. I. A colored curable resin composition was obtained in the same manner as in Example 9, except that Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant) was used.

For the colored curable resin compositions obtained in Examples 9 to 15 and Comparative Example 2, in the same manner as in Example 1, a color filter (colored pattern) was prepared, film thickness was measured, and a curable composition for overcoat was prepared. was prepared, and the heat resistance of the laminated film was evaluated. Table 3 shows the film thickness measurement results of Examples 9 to 15 and Comparative Example 2, and the heat resistance evaluation results of the laminated films. A smaller ΔE*ab means a smaller color change.

INDUSTRIAL APPLICABILITY The colored curable resin composition of the present invention can be used for producing color filters used in display devices such as liquid crystal display devices, organic EL devices, and electronic paper, and solid-state imaging devices.

Claims (4)

Contains a coloring agent, an alkali-soluble resin, a polymerizable compound and a polymerization initiator,
The colorant contains a xanthene compound having a carboxy group and a compound represented by formula (A1),
The colored curable resin composition , wherein the xanthene compound having a carboxyl group is a compound represented by formula (A2) .

[In the formula (A1),
A ^1a and A ^2a each independently represent an optionally substituted phenylene group.
L ^1a and L ^2a each independently represent a divalent hydrocarbon group having 1 to 12 carbon atoms, and —CH ₂ — contained in the hydrocarbon group is —O—, —SO ₂ — or —NR ^11a - may be substituted.
R ^1a to R ^6a each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms. R ^11a represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[In formula (A2),
R ^1b to R ^4b are each independently a hydrogen atom, an optionally substituted C 6-10 aromatic hydrocarbon group, or an optionally substituted C 1-20 and --CH ₂ -- contained in the saturated hydrocarbon group may be replaced with --O--, --CO-- or --NR ^11b --. R ^1b and R ^2b may together form a ring containing a nitrogen atom, and R ^3b and R ^4b may together form a ring containing a nitrogen atom.
R ^6b and R ^7b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
At least one of R ^1b to R ^4b represents an aromatic hydrocarbon group having -COOH and having 6 to 10 carbon atoms or a saturated hydrocarbon group having -COOH and having 1 to 20 carbon atoms. ] 2. The colored curable resin composition according to claim 1 , wherein said coloring agent further contains a blue pigment. A color filter formed from the colored curable resin composition according to claim 1 or 2 . A display device comprising the color filter according to claim 3 .