JP2013053292A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition which can manufacture a color filter showing high contrast.SOLUTION: The colored curable resin composition contains a colorant, a resin, a polymerizable compound and a polymerization initiator. The colorant contains a xanthene dye and an anthraquinone dye.

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 xanthene dye and C.I. I. A colored curable resin composition containing only pigment blue 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.

The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
A colored curable resin composition, wherein the colorant is a colorant comprising a xanthene dye and an anthraquinone dye.
[2] The colored curable resin composition according to [1], wherein the content of the anthraquinone dye is 0.1% by mass or more and 70% by mass or less based on the total amount of the colorant.
[3] The colored curable resin composition according to [1] or [2], wherein the colorant further includes a 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 according to [4].

  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 is a colored curable resin composition containing a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). ) Contains a xanthene dye (Aa) and an anthraquinone dye (Ab). Furthermore, it is preferable to contain a solvent (E) and / or a leveling agent (F).
The colored curable resin composition of the present invention can produce a high-contrast color filter by containing a xanthene dye (Aa) and an anthraquinone dye (Ab) as the colorant (A).

<Colorant (A)>
The colorant (A) contains a xanthene dye (Aa) and an anthraquinone dye (Ab). Furthermore, it is preferable that a pigment (Ad) is included. Further, a dye different from the xanthene dye (Aa) and the anthraquinone dye (Ab) (hereinafter sometimes referred to as “dye (Ac)”) may be included.

  The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) 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. Those that are soluble in organic solvents are preferred.

  Among these, as the xanthene dye (Aa), 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 the compound (1a), the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye (Aa).

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、互いに独立に、水素原子、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。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⁺、−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以上の整数である場合、複数のＲ⁵は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、ハロゲン原子を表す。
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、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
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、該飽和脂肪族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、互いに独立に、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 are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent having 6 to 10 carbon atoms. Represents a monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon The hydrogen atom contained in the group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, —CO— or —NR ¹¹ —. It may be replaced with. 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 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
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 an integer of 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
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.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
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 is contained in the saturated aliphatic hydrocarbon group − CH ₂ — may be replaced by —O—, —CO—, —NH— or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded to each other and contain 3 to 10 members containing a nitrogen atom. A heterocyclic ring may be formed.
R ¹¹ independently 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 representing 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 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 the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, are mentioned.

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.

Moreover, as a substituent which the C1-C20 monovalent saturated hydrocarbon group showing R < ⁹ >, R < ¹⁰ > may have, a hydroxyl group and a halogen atom are mentioned.

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 that represents the 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 representing 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.

  As the compound (1a), a compound represented by the formula (2a) (hereinafter sometimes referred to as “compound (2a)”) is more preferable. Compound (2a) may be a tautomer thereof. When the compound (2a) is used, the content of the compound (2a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

［式（２ａ）中、Ｒ²¹〜Ｒ²⁴は、それぞれ独立に、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価の置換基を有していてもよい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以上の整数である場合、複数のＲ²⁵は同一であるか相異なる。
ａ１は、０又は１の整数を表す。
Ｘ１は、ハロゲン原子を表す。
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⁺を表す。
Ｒ²⁷は、それぞれ独立に、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 have a hydrogen atom, —R ^26, or a monovalent substituent having 6 to 10 carbon atoms that may have a substituent. Represents a good aromatic hydrocarbon group. 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 an integer of 2 or more, the plurality of R ²⁵ are the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms representing R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in 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 representing 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), a color filter with less generation of foreign matters from the colored curable resin composition of the present invention containing the compound (2a) in which R ²⁷ is these groups Can be formed.

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

  As the compound (1a), a dye containing a compound represented by the formula (3a) (hereinafter sometimes referred to as “compound (3a)”) is more preferable. Compound (3a) may be a tautomer thereof. When the compound (3a) is used, the content of the compound (3a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

［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以上である場合、複数のＲ³³は同一でも異なってもよく、ｑが２以上である場合、複数のＲ³⁴は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 representing 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, and more preferably a methyl group.

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

Examples of compound (1a) include compounds represented by formula (1-1) to formula (1-42), respectively. In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. The compound represented by Formula (1-1) to Formula (1-29) corresponds to Compound (2a), and the compound represented by Formula (1-30) to Formula (1-42) is Compound (3a). It corresponds to.

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), and formula (1-12).
Moreover, the compound represented by Formula (1-30)-Formula (1-39) is preferable at the point which is excellent in the solubility to an organic solvent.

  As the xanthene dye (Aa), 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 Industry Co., 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.

An anthraquinone dye (Ab) is a dye containing a compound having an anthraquinone skeleton in the molecule. As an anthraquinone dye (Ab), for example,
C. I. Solvent Yellow 117, 163, 167, 189,
C. I. Solvent orange 77, 86,
C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Red 80,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Yellow 51,
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Red 3, 11,
C. I. Modern Blue 8
Etc. The anthraquinone dye (Ab) is preferably one that dissolves in an organic solvent, and more preferably a blue, violet, or red anthraquinone dye.

  Among these, as the anthraquinone dye (Ab), a dye containing a compound represented by the formula (1b) (hereinafter sometimes referred to as “compound (1b)”) is preferable. When using the compound (1b), the content of the compound (1b) in the anthraquinone dye (Ab) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1b) as the anthraquinone dye (Ab).

［式（１ｂ）中、Ａは、ヒドロキシ基又は−ＮＨ−Ｒ^５２を表す。
Ｒ^５１及びＲ^５２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１〜１０の脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の脂環式炭化水素基又は式（１ｂ’）

（式（１ｂ’）中、Ｒ^５３は、炭素数１〜６のアルキル基、ハロゲン原子、−ＳＯ_３Ｈ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^５４、−ＮＨＣＯＲ^５４、−ＳＯ_３Ｒ^５４又は−ＳＯ_２ＮＲ^５４Ｒ^５５を表す。
Ｒ^５４は、炭素数１〜１０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、ヒドロキシ基又はアミノ基で置換されていてもよい。
Ｒ^５５は、水素原子、炭素数１〜１０の飽和炭化水素基を表す。
ｒは、０〜５の整数を表す。ｒが２以上の場合、複数のＲ^５３は同一でも異なってもよい。
Ｘ^５１は、単結合又は炭素数１〜６のアルカンジイル基を表す。）
で表される基を表す。］
化合物（１ｂ）が、−ＳＯ_３Ｈ及び／又は−ＣＯ_２Ｈを有する場合、これらは塩（例えば、Ｎａ塩やＫ塩）を形成していてもよい。

[In the formula (1b), A represents a hydroxy group or —NH—R ⁵² .
R ⁵¹ and R ⁵² are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted group having 3 to 10 carbon atoms. An alicyclic hydrocarbon group or formula (1b ′)

(In the formula (1b ′), R ⁵³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, —SO ₃ H, —CO ₂ H, —CO ₂ R ⁵⁴ , —NHCOR ⁵⁴ , —SO ₃ R ⁵⁴ or It represents a -SO ₂ NR ⁵⁴ R ^55.
R ⁵⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, a hydroxy group or an amino group.
^R55 represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
r represents an integer of 0 to 5. When r is 2 or more, the plurality of R ⁵³ may be the same or different.
X ⁵¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. )
Represents a group represented by ]
When the compound (1b) has —SO ₃ H and / or —CO ₂ H, these may form a salt (for example, Na salt or K salt).

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms representing R ⁵¹ and R ⁵² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, Examples include decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and the like.
Examples of the substituent that these aliphatic hydrocarbon groups may have include a hydroxy group and a halogen atom.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms representing R ⁵¹ and R ⁵² include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, and the like. .
Examples of the substituent that these alicyclic hydrocarbon groups may have include a hydroxy group and a halogen atom.

Examples of the alkyl group having 6 to 10 carbon atoms representing R ⁵³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Isopentyl group, neopentyl group and the like.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms representing R ⁵⁴ and R ⁵⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Linear alkyl group such as a group; branched alkyl group such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group And saturated alicyclic hydrocarbon groups such as a tricyclodecyl group.

Examples of —CO ₂ R ⁵⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —NHCOR ⁵⁴ include an N-acetylamino group, an N-propanoylamino group, an N-butyrylamino group, an N-isobutyrylamino group, and an N-pivaloylamino group.

Examples of —SO ₃ R ⁵⁴ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

Examples of —SO ₂ NR ⁵⁴ R ⁵⁵ include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, and N-butylsulfamoyl group. 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-cyclopentyl Rufamoyl group, N-cyclohexylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfa Moyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1, N-1-substituted sulfamoyl groups such as 5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- (5-aminopentyl) 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.

The alkanediyl group having 1 to 6 carbon atoms representing the X ^51, for example, methylene group, ethylene group, propane-1,3-diyl, propane-1,2-diyl group, butane-1,4-diyl group , Pentane-1,5-diyl group, hexane-1,6-diyl group, ethane-1,1-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2 -Methylpropane-1,2-diyl group, pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group and the like.

  Examples of compound (1b) include compounds represented by formula (2-1) to formula (2-13).

  Examples of the anthraquinone dye (Ab) include C.I. I. Solvent Blue 35 (compound represented by formula (2-4)), C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80 (compound represented by Formula (2-11)), C.I. I. Solvent Blue 104 (a compound represented by the formula (2-12)) and C.I. I. Solvent blue 122 (a compound represented by the formula (2-13)) is preferable. These anthraquinone dyes can form a high-contrast coating film or pattern, and generate less foreign matter.

  The dye (Ac) is not particularly limited as long as it is a dye different from the xanthene dye (Aa) and the anthraquinone dye (Ab), and is an oil-soluble dye, an acid dye, a basic dye, a direct dye, a mordant dye, or an acid dye. Examples include dyes such as amine salts and sulfonamides of acid dyes. For example, dyes that are classified in the Color Index (published by The Society of Dyers and Colorists), that is, compounds other than pigments, and dyeing notes (color dyeing company) And publicly known dyes described in the above. Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline dye and nitro dye And dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent red 45, 49, 125, 130;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. 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, 34, 35, 37, 42, 44, 50, 57, 66, 73, 80, 88, 91, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257,258,260,261,266,268,270,274,277,280,281,308,312,315,316,339,341,345,346,349,382,383,394,401,412 417, 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, 17, 19;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,
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 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, 6, 8, 15, 22, 25, 41, 57, 71, 76, 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, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Examples include modern dyes.

The pigment (Ad) is not particularly limited, and a known pigment can be used, and examples thereof include compounds classified as pigments by the 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. When the colored curable resin composition of the present invention is prepared as a blue colored curable resin composition, by including the above-mentioned pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter. Will be better.
These pigments may be used alone or in combination of two or more.

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, and more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (Ad). When the amount of the pigment dispersant used is in the above range, a pigment dispersion with a uniform dispersion tends to be obtained.

The content of the xanthene dye (Aa) is preferably 0.1% by mass or more and 70% by mass or less, and more preferably 0.5% by mass or more and 50% by mass or less with respect to the total amount of the colorant (A).
The content of the anthraquinone dye (Ab) is preferably 0.1% by mass or more and 70% by mass or less, and more preferably 0.5% by mass or more and 50% by mass or less with respect to the total amount of the colorant (A).
When the colorant (A) contains the pigment (Ad), the content of the pigment (Ad) is preferably 10% by mass or more and 99.8% by mass or less, and 30% by mass with respect to the total amount of the colorant (A). More preferred is 99% by mass or less.
When the colorant (A) contains a dye (Ac), the content of the dye (Ac) is preferably 0.1% by mass or more and 50% by mass or less with respect to the total amount of the colorant (A). More preferably, it is at least 30% by mass.

When the colorant (A) is a colorant composed of a xanthene dye (Aa), an anthraquinone dye (Ab), and a pigment (Ad), these content ratios are respectively
Xanthene dye (Aa): 0.1% by mass or more and 70% by mass or less Anthraquinone dye (Ab); 0.1% by mass or more and 70% by mass or less Pigment (Ad); 29.9% by mass or more and 99.8% by mass or less Preferably,
Xanthene dye (Aa); 0.5 mass% to 50 mass% Anthraquinone dye (Ab); 0.5 mass% to 50 mass% Pigment (Ad); 49.5 mass% to 99 mass% Is more preferable.

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass with respect to the total amount of the solid content. 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. Examples of the resin (B) 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 (a1) 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.

  (B1) may be, for example, a monomer (b1-1) having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon (hereinafter referred to as “(b1-1)”) ), A monomer (b1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon (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 Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[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 alkanediyl groups 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 the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) or Formula (I-11) to Formula (I-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II-11) to Formula (II-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (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.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. 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. .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 Bicyclo unsaturated 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.
Of these, styrene, 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.

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 photosensitive 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 photosensitive resin composition of the present invention. Therefore, the manufacturing process of the colored photosensitive 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 (highmic acid anhydride) and the like. It is done. 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 acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resin such as resin obtained by adding glycidyl (meth) acrylate to acid copolymer [K4]; resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with the polymer [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and tetrahydro Examples thereof include a resin [K6] such as a resin reacted with phthalic anhydride.
These resins may be used alone or in combination of two or more.

  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 in the above range, a colored pattern can be formed, and the resolution and remaining film ratio of the colored pattern 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. The polymerizable compounds may be used alone or in combination of two or more.
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. More preferred is a polymerization initiator containing a sulfur compound.

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（登録商標）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, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {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 (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by 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 (registered trademark) 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-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Thenyl] -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 and 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 (trialkoxy) Phenyl) 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, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- 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. If the content of the polymerization initiator (D) is in the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

In addition to the polymerization initiator (D), a polymerization initiation assistant (D1) may further be included. 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.
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, with thioxanthone compounds being preferred.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl 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, and 4,4′-bis (diethylamino) benzophenone is preferred. 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
The polymerization initiation assistants may be used alone or in combination of two or more.

  When these polymerization initiation assistants (D1) are used, the amount used 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.

<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-,- Solvents not containing CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

  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.

These solvents may be used alone or in combination of two or more.
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 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 flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<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.

These surfactants may be used alone or in combination of two or more.
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 0.01 mass% and not more than 0.05 mass%. When the leveling agent (F) content is in the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention may contain various additives such as a filler, other polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. .

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
The xanthene dye (Aa), the anthraquinone dye (Ab), and the dye (Ac) used as necessary may be dissolved in part or all of the solvent (E) in advance to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
When the pigment (Ad) is included, the pigment (Ad) is previously mixed with a part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Is preferred. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion, the remainder of the colorant (A), the remainder of the resin (B), the remainder of the polymerizable compound (C), the polymerization initiator (D) and the solvent (E), and as necessary The target colored curable resin composition can be prepared by mixing the leveling agent (F) used, the polymerization initiation assistant (D1), and other components so as to have a predetermined concentration.
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 (for example, a color filter layer formed on the substrate with a colored curable resin composition), a resin layer, a transistor, a circuit, or 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 photosensitive 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 (C) and the like contained in the colored composition layer, For example, heating is performed at a temperature of 100 to 300 ° C., preferably 150 to 230 ° C., for example, for 1 to 120 minutes, preferably 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 elemental analysis (VARIO-EL; (Elemental Co., Ltd.)).

[Synthesis Example 1]
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 in a flask equipped with a condenser and a stirrer. 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 exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried at 60 ° C. under reduced pressure, and dye (Aa-1) (compounds represented by formula (A1-1) to formula (A1-8)). 11.3 parts of a mixture were obtained.

[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 residue of suction filtration and dried to obtain 24 parts of a compound represented by the formula (1-30). The yield was 80%.

The structure of the compound represented by the formula (1-30) was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−３８）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 (1-38) 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 compound represented by formula (1-38) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.9
Exact Mass: 658.9

[Synthesis Example 4]
12 parts of the compound represented by the formula (1x), 60 parts of N-methyl-2-pyrrolidone, and 12.6 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and the resulting mixture is mixed at 60 ° C. with 5 parts. Stir for hours. The reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 12.4 parts of a compound represented by the formula (1-27). The yield was 83%.

Identification of compound represented by formula (1-27) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 503.4
Exact Mass: 502.2

[Synthesis Example 5]
15 parts of the compound represented by the formula (1x), 75 parts of N-methyl-2-pyrrolidone and 25.8 parts of decahydroquinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, and the resulting mixture is 110 ° C. For 24 hours. The reaction solution was cooled to room temperature, added to a mixed solution of 600 parts of water and 100 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour. The precipitated crystals were obtained as a suction filtration residue and dried to obtain 19.5 parts of a compound represented by the formula (1-29). The yield was 86%.

Identification of compound represented by formula (1-29) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 611.4
Exact Mass: 610.3

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０質量部を乳酸エチル２２５質量部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、９．１×１０^３、分子量分布は２．１、固形分２６質量％、固形分酸価１２０ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。樹脂Ｂ１は下記に示す構造単位を有する。

[Synthesis Example 6]
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 by mass of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Subsequently, 46 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 185 parts by mass of ethyl lactate, and the solution is added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC.

On the other hand, a solution prepared by dissolving 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. did. After completion of the dropwise addition of the polymerization initiator solution, the temperature was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw was 9.1 × 10 ³ , the molecular weight distribution was 2.1, and the solid content A resin B1 solution having 26% by mass and a solid content acid value of 120 mg-KOH / g was obtained. Resin B1 has the structural units shown below.

[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., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 136 g of propylene glycol monomethyl ether acetate, a solution obtained by adding 3.6 g of 2,2′-azobisisobutyronitrile 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 B2 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.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部をプロピレングリコールモノメチルエーテルアセテート２２５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、９．１×１０^３、分子量分布が２．１６、固形分３４．８％、固形分換算の酸価は８１ｍｇＫＯＨ／ｇの樹脂Ｂ３溶液を得た。樹脂Ｂ３は下記に示す構造単位を有する。

[Synthesis Example 8]
Nitrogen was flowed at 0.02 L / min into a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel to form a nitrogen atmosphere, 305 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. did. Next, 60 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound is mixed in a molar ratio of 50:50.) A solution is prepared by dissolving in 440 parts and 140 parts of propylene glycol monomethyl ether acetate. It was dripped in the flask kept at 70 degreeC.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After the addition of the solution of the polymerization initiator is completed, 4 hours, kept at 70 ° C., and then cooled to room temperature, a weight average molecular weight Mw, 9.1 × 10 ^3, the molecular weight distribution is 2.16, solids A resin B3 solution having an acid value of 34.8% in terms of solid content of 81 mgKOH / g was obtained. Resin B3 has the structural units shown below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example 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)
(A) Colorant: C.I. I. Pigment Blue 15: 6 (pigment) 24 parts Acrylic pigment dispersant 6.1 parts Propylene glycol monomethyl ether acetate 163 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
(A) Colorant: Dye (A1-a) (xanthene dye) 1.8 parts (A) Colorant: C.I. I. Solvent Blue 35 (Sudan Blue II; manufactured by Aldrich; anthraquinone dye) 1.8 parts (B) Resin: Resin B1 (solid content conversion) 60 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark)) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01) ; Manufactured by BASF) 5 parts (F) Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.08 parts (E) Solvent: ethyl lactate 682 parts (E) Solvent: Colored curable resin composition by mixing 8 parts of propylene glycol monomethyl ether acetate It was obtained.

<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 cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used, and 150 mJ / cm in an air atmosphere. 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 30 ° C. for 30 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 Tables 3 and 4.

<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; made by Osaka Co., Ltd., color difference meter BM-5A; made by Topcon Co., Ltd., light source; F-10, polarizing film; made by Osaka 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 Tables 3 and 4.

[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: Dye (Aa-1) (Xanthene dye) 3.5 parts (B) Resin: Resin B2 solution 157 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. product) ) 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. .

Examples 2-15
A colored curable resin composition was obtained by performing the same operation as in Example 1 so that the compositions shown in Table 1 and Table 2 were obtained.

In Tables 1 and 2, “Ad-1 ¹⁾ ” was mixed with an acrylic pigment dispersant and an amount of propylene glycol monomethyl ether acetate described in the “E-1 ³⁾ ” column and dispersed in advance.
"E-1 ^2)" column represents the total content of propylene glycol monomethyl ether acetate.
In Table 1 and Table 2, each component represents the following. Moreover, resin (B) represents the mass part of solid content conversion.
Xanthene dye (Aa): Aa-1: Dye (Aa-1)
Xanthene dye (Aa): Aa-2: Compound represented by formula (1-30) Xanthene dye (Aa): Aa-3: Compound represented by formula (1-38) Xanthene dye (Aa): Aa- 4: C.I. I. Acid Red 52 (manufactured by Tokyo Chemical Industry Co., Ltd.)
Xanthene dye (Aa): Aa-5: Compound represented by formula (1-27) Xanthene dye (Aa): Aa-6: Compound represented by formula (1-29) Anthraquinone dye (Ab): Ab- 1: C.I. I. Solvent Blue 35 (Sudan Blue II; manufactured by Aldrich)
Anthraquinone dye (Ab): Ab-2: C.I. I. Solvent Blue 45 (Savinyl Blue RS; manufactured by Clariant)
Anthraquinone dye (Ab): Ab-3: C.I. I. Acid Blue 80 (Coomassie (registered trademark) Blue B 150; manufactured by ICI)
Anthraquinone dye (Ab): Ab-4: C.I. I. Solvent Blue 104 (Polysynthren Blue RBL P; manufactured by Clariant)
Anthraquinone dye (Ab): Ab-5: C.I. I. Solvent Blue 122 (Polysynthren Blue R; manufactured by Clariant)
Pigment (Ad): Ad-1: C.I. I. Pigment Blue 15: 6
Resin (B): B-1: Resin B1
Resin (B): B-2: Resin B2
Resin (B): B-3: Resin B3
Polymerizable compound (C): dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): D-1: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; O-acyloxy Compound)
Polymerization initiator (D): D-2: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one (Irgacure (registered trademark) 907; manufactured by BASF; alkylphenone compound)
Polymerization initiation aid (D1): 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-S; manufactured by Nippon Kayaku Co., Ltd .; thioxanthone compound)
Solvent (E): E-1: Propylene glycol monomethyl ether acetate Solvent (E): E-2: Ethyl lactate Solvent (E): E-3: Propylene glycol monomethyl ether Solvent (E): E-4: 4-hydroxy -4-Methyl-2-pentanone Leveling (F): Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

  The colored curable resin compositions of Examples 2 to 15 and Comparative Example 1 obtained as described above were evaluated in the same manner as in Example 1. The results are shown in Tables 3 and 4.

  According to the colored curable resin composition of an Example, it was confirmed that the obtained 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 (5)

Including a colorant, a resin, a polymerizable compound and a polymerization initiator,
A colored curable resin composition, wherein the colorant is a colorant comprising a xanthene dye and an anthraquinone dye.   The colored curable resin composition according to claim 1, wherein the content of the anthraquinone dye is 0.1% by mass or more and 70% by mass or less based on the total amount of the colorant.   The colored curable resin composition according to claim 1 or 2, wherein the colorant further comprises a pigment.   The color filter formed with the colored curable resin composition as described in any one of Claims 1-3.   A display device comprising the color filter according to claim 4.

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