JP2018136367A - Colored curable resin composition, color filter, and display including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition with which a colored cured coating with good film thickness retention can be formed even with a relatively small amount of exposure, a color filter formed from the colored curable resin composition, and a display including the color filter.SOLUTION: There are provided a colored curable resin composition that contains a coloring agent (A), resin (B), polymerizable compound (C), and polymerization initiator (D), where the coloring agent (A) contains a dye, and the polymerization initiator (D) contains a polymerization initiator represented by the formula (D-1), and a color filter and a display using the same.SELECTED DRAWING: None

Description

  The present invention relates to a colored curable resin composition, a color filter, and a display device including the same.

The color filter is formed by applying and drying a colored curable resin composition, followed by exposure, development, and heat treatment (baking). The colored curable resin composition usually contains a polymerization initiator in order to allow the coating film to be cured by exposure.
As the polymerization initiator, a photopolymerization initiator such as an oxime compound is known (Patent Document 1).

JP 2011-116803 A

  The present invention relates to a colored curable resin composition capable of forming a colored cured coating film having a good film thickness retention rate even when the exposure amount is relatively small, and a color filter formed from the colored curable resin composition And a display device including the color filter.

  The present invention provides the following colored curable resin composition, color filter, and display device.

[1] Including a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
The colorant (A) contains a dye,
A colored curable resin composition in which the polymerization initiator (D) includes a polymerization initiator represented by the formula (D-1).

[Wherein, R ^d1 and R ^d2 each independently represent a hydrogen atom, a chain alkyl group which may have a substituent, or a cyclic organic group which may have a substituent, and R ^d1 And R ^d2 together may form a ring,
R ^d3 represents a monovalent organic group,
R ^d4 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group;
dm represents 0 or 1. ]
[2] The colored curable resin composition according to [1], wherein the dye includes a dye having a xanthene skeleton.
[3] A color filter formed from the colored curable resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

A colored curable resin composition capable of forming a colored cured coating film having a good film thickness retention rate even when the exposure amount is relatively small, a color filter formed from the colored curable resin composition, and the color A display device including a filter can be provided.
According to the present invention, even when the exposure amount is low, it is possible to form a film thickness equivalent to that when the exposure amount is high, and the exposure time tends to be shortened, so the productivity of the color filter tends to be improved.

<Colored curable resin composition>
The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), the colorant (A) contains a dye, and polymerization starts. Agent (D) contains a polymerization initiator represented by formula (D-1).
According to the colored curable resin composition, a colored cured coating film having good film thickness retention can be formed even when the exposure amount is relatively small. Therefore, according to the colored curable resin composition, the colored curable resin composition is formed by applying and drying the colored curable resin composition, then exposing, developing as necessary, and then heat-treating (baking). Regarding the coating film, even when the exposure amount is relatively small, the retention rate of the film thickness when compared with the case where the exposure amount is sufficiently high can be increased.
In addition, unless otherwise indicated, the compound illustrated as each component in this specification can be used individually or in combination of multiple types.

[1] Colorant (A)
In the colored curable resin composition of the present invention, the colorant (A) contains a dye.
The dye is not particularly limited, and a known dye can be used, and examples thereof include a solvent dye, an acid dye, a direct dye, and a mordant dye.
Examples of the dye include compounds classified as having a hue other than pigment in the color index (published by The Society of Dyers and Colorists), and known dyes described in dyeing notes (color dyeing company). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye And dyes, quinoline dyes and nitro 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, 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 41 , 418,422,426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 29,234,236,242,243,256,259,267,269,278,280,285,290,296,315,324: 1,335,340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, 104, 105, 106, 109, 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 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229 236,237,238,242,243,244,245,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic violet 2;
C. I. Basic Red 9;
C. I. C. of Basic Green 1 etc. I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. C. of Reactive Red 36, etc. I. Reactive dyes,
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, 27, 29, 30, 32, 33, 36, 37, 38 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 1, 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Examples include vat dyes.

  These dyes may be appropriately selected according to the desired spectral spectrum of the color filter.

From the viewpoints of solvent resistance, heat resistance, and / or good lightness, the colored curable resin composition of the present invention has a dye having a xanthene skeleton as a dye (hereinafter, the dye is referred to as a xanthene dye). Preferably).
As the xanthene dye, C.I. I. Acid Red 51, 52, 87, 92, 289, 388, C.I. I. Acid Violet 9, 30, C.I. I. Basic Red 8, C.I. I. Modern Red 27, Rose Bengal B, Sulforhodamine G, Rhodamine 6G, xanthene dye described in JP 2010-32999 A, xanthene dye described in Japanese Patent No. 4492760, and the like. The colorant (A) can contain one or more xanthene dyes.
The xanthene dye can contain a compound represented by the formula (1) (hereinafter also referred to as “compound (1)”).

In Expression ^(1), R 1 to R ⁴ are each independently hydrogen atom, or a monovalent aromatic hydrocarbon group -R ⁸ or 6 to 10 carbon atoms, or, ^{R 1} and ^{R 2} R ³ and R ⁴ together form a ring containing a nitrogen atom. Hydrogen atoms contained in the aromatic hydrocarbon group, a halogen _{^{atom, -R 8, -OH, -OR 8}} , -SO 3 -, -SO 3 H, -SO 3 - M +, -CO 2 H, - It may be substituted with CO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ . Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - M +, -CO 2 H, -CO 2 - M +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
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 from each other.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
M ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ . X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
a represents 0 or 1.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —S—, —O—, —CO— or —NR ¹¹ —. R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. When a plurality of R ¹¹ are present, all or part of them may be the same.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is substituted with —OH or a halogen atom. And —CH ₂ — contained in the saturated aliphatic hydrocarbon group may be replaced by —S—, —O—, —CO—, —NH— or —NR ⁸ —. , R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.
Monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ¹ to R ⁴ are, as a _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - M + and _-SO 2 ^NR 9 ^{R 10} it is preferable to have at least one member selected from the group consisting of, _-SO ³ - to have at least one member selected from the group consisting of ^{M +} and _-SO 2 ^NR 9 ^{R 10} More preferred. _-SO ³ in this case - ^{M + _{Examples, -SO 3 - + N (R}} 11) 4 are preferred. When R ^{1 to} R ⁴ are these groups, it is advantageous for forming a color filter having 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 rings. In the following rings, * represents a bond.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{8 to} R ¹¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, and hexyl. Group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group, etc. alkyl group having 1 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl C3-C20 cycloalkyl groups, such as a group, a cyclooctyl group, and a tricyclodecyl group.

Regarding R ⁸ , the aromatic hydrocarbon group having 6 to 10 carbon atoms in which the hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted includes phenyl group, toluyl group, xylyl Group, mesityl group, propylphenyl group, butylphenyl group and the like. Examples of the group in which —CH ₂ — contained in R ⁸ is replaced by —S—, —O—, —CO—, or —NR ¹¹ — include the following groups. In the following groups, * represents a bond.

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

Examples of the group represented by —SO ₂ NR ⁹ R ¹⁰ include groups represented by the following formulae. In the following groups, * represents a bond.

In the above formula, X ⁰ and X ² each independently represent a halogen atom. Examples of the halogen atom in X ⁰ and X ² include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ in the formula (1) include a benzyl group, a phenylethyl group, and a phenylbutyl group.

M ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ . ⁺ N (R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ¹¹ . The total number of carbon atoms of the four ^{R 11} is preferably 20 to 80, 20 to 60 is more preferable.

  A xanthene dye can also contain the compound represented by Formula (2).

[In the formula (2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group. hydrogen atoms _{^{are, -SO 3 -, -SO 3 -}} M a +, -SO 3 H, optionally substituted by -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
a1 represents 0 or 1. m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ may be the same or different. M ^{a +} represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁵ _is, ^-SO 3 _- represents a M a +, -SO ₃ H or _{^{SO 2 NHR 26 -, -SO 3}} .
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. Four R < ²⁷ > represents a C1-C20 monovalent | monohydric saturated hydrocarbon group or benzyl group mutually independently. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ in the formula (2) include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ . It is done. Among them, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are substituted. when a group is _{^{substituted, -SO 3 -, -SO 3 -}} M +, -SO 3 H, is preferably -SO ^{3 R 26} or _-SO 2 ^{NHR 26.} Furthermore, R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon groups are: more preferably M ⁺ or those which may be substituted with _-SO 2 ^{NHR 26 -} _{-SO 3.} When R ^{21 to} R ²⁴ are these groups, it is advantageous for forming a color filter having excellent heat resistance.
Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ include the same groups as those exemplified as the saturated hydrocarbon group in R ^{8 to} R ¹¹ . ^{-R 26} in ^R 21 ^{to R 24} in the formula (2) each independently represent a hydrogen atom, a methyl group or an ethyl group.
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, 2- More preferred is an ethylhexyl group.
M ^{a +} is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ . ⁺ N (R ²⁷ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ²⁷ . The total number of carbon atoms of the four ^{R 27} is preferably 20 to 80, 20 to 60 is more preferable.
The xanthene dye can contain any one or more of the compounds represented by formula (1-1) to formula (1-16). In formulas (1-1) to (1-16), Ra represents a 2-ethylhexyl group.

  Among these compounds, C.I. I. Acid Red 289 sulfonamidated product or C.I. I. A quaternary ammonium salt of Acid Red 289 is more preferable. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12), respectively.

The compound represented by formula (1-1) to formula (1-16) is, for example, a dye having —SO ₂ Cl obtained by chlorinating a dye or dye intermediate having —SO ₃ H by a conventional method. Alternatively, it can be produced by reacting a dye intermediate with an amine represented by R ⁸ —NH ₂ .
Moreover, it can manufacture also by the method with which the pigment | dye manufactured by the method of the upper right column-lower left column of Unexamined-Japanese-Patent No. 3-78702 3 is made to react with an amine after chlorination like the above.

  A xanthene dye can also contain any one or more of the compounds represented by Formula (1-17)-Formula (1-31).

The compounds represented by the formula (1-17) to the formula (1-31) can be produced according to the methods described in the upper right column to the lower left column of the third page of JP-A-3-78702. Examples of such a method include a method of reacting the compound represented by the formula (1a) with the compound represented by the formula (1b) and the compound represented by the formula (1c). In formula (1b) and formula (1c), R ^{1 to} R ⁴ each represent the same meaning as described above.

Examples of other xanthene dyes include xanthene dyes described in JP-A-2006-027075. As a xanthene dye described in JP-A-2006-027075, in formula (1), a is 0, and at least one of R ^{1 to} R ⁴ is a group represented by formula (i). Compounds.
* -R ⁵⁰ -Si (R ²⁹ ) ₃ (i)
[In formula (i), R ²⁹ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents a bond to a nitrogen atom. The plurality of R ²⁹ may be the same or different.
R ⁵⁰ represents an alkanediyl group having 1 to 10 carbon atoms, and —CH ₂ — constituting the alkanediyl group is —O—, —CO—, —NR ⁵¹ —, —OCO—, —COO—, — It may be substituted with OCONH-, -CONH- or -NHCO-.
R ⁵¹ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms. ]

Examples of the alkyl group having 1 to 4 carbon atoms in R ²⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms in R ²⁹ include a methoxy group, an ethoxy group, a propoxy group, and a tert-butoxy group.
R ²⁹ is preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a methoxy group or an ethoxy group.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ⁵⁰ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, and 2-methyltriene. Examples include a methylene group, an isopentylene group, an isohexylene group, an isooctylene group, a 2-ethylhexylene group, preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms. Is mentioned.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁵¹ 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, a decyl group, and a dodecyl group. A linear alkyl group having 1 to 20 carbon atoms, such as a group, hexadecyl group and icosyl group; carbon such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group A branched alkyl group having 3 to 20 carbon atoms; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group. It is done.

Preferable examples of the group represented by the formula (i) include a group represented by the formula (ia).
* — (CH ₂ ) _n —Si (OR ³⁹ ) ₃ (ia)
[In formula (ia), n represents an integer of 1 to 8, R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a bond with a nitrogen atom. ]

Examples of the alkyl group having 1 to 4 carbon atoms for R ³⁹ include a methyl group, an ethyl group, a propyl group, and a butyl group, and a methyl group, an ethyl group, and a propyl group are preferable.
n is preferably an integer of 1 to 4, more preferably an integer of 1 to 3.

As described above, the colorant (A) can contain a dye other than the xanthene dye.
As a dye other than the xanthene dye, the colorant (A) may contain a dye insoluble in water or an organic solvent by a rake agent.

The colorant (A) can further contain a pigment in addition to the dye. The pigment is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
The colorant (A) can contain one or more pigments.
When the colorant (A) further contains a color pigment, the transmission spectrum can be easily optimized, and the light resistance and solvent resistance of the color filter can be improved.

As a coloring pigment,
C. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231;
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. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 16, 60, 80;
C. 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, 59, 62, 63;
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.
As the red pigment, a pigment having a diketopyrrolopyrrole skeleton described in JP2013-14750A can also be used.

The various pigments used in the preparation of the colored curable resin composition are preferably in the state of a dispersion that is uniformly dispersed in a solvent. The pigment preferably has a uniform particle size. The dispersion can be obtained by mixing a pigment and a solvent. If necessary, a pigment dispersant may be mixed. By carrying out a dispersion treatment by containing a pigment dispersant, it is possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solvent.
Commercially available surfactants can be used as the pigment dispersant, including silicone, fluorine, ester (including polyester), cationic, anionic, nonionic, amphoteric, polyester, polyamine, Examples of the surfactant include acrylic. Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (manufactured by BASF Japan Co., Ltd.), and Ajisper (registered trademark) ) (Manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by Big Chemie) and the like. Only one pigment dispersant may be used, or two or more pigment dispersants may be used in combination.

  When a pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion in a uniform dispersion state tends to be obtained.

  It does not specifically limit as a solvent which comprises a pigment dispersion liquid, The solvent similar to the below-mentioned solvent (E) which can be contained in a colored curable resin composition is mentioned. Among them, the solvents are 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, 3-methoxybutyl acetate, 3-methoxy- 1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Must be butyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc. Preferred.

  Although the usage-amount of a solvent is not specifically limited, The density | concentration of the solid content in a pigment dispersion liquid is preferably 3-20 mass%, More preferably, it is the quantity used as 5-18 mass%.

  Various pigments used in the preparation of the colored curable resin composition include rosin treatment, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group is introduced, a polymer compound, if necessary Grafting to the pigment surface by etc., atomization treatment by sulfuric acid atomization method, etc., washing treatment with organic solvent or water to remove impurities, removal treatment by ion exchange method of ionic impurities etc. It may be.

The total content of the colorant (A) in the colored curable resin composition is usually 10 to 60% by mass in 100% by mass of the solid content of the colored curable resin composition, but from the viewpoint of the lightness of the color filter. , Preferably it is 15-50 mass%. From the viewpoint of easy formation of the resist pattern, the total content is 100% by mass or less, preferably 45% by mass or less, of the solid content of the colored curable resin composition.
In the present specification, the “solid content of the colored curable resin composition” refers to all components other than the solvent (E) among the components contained in the colored curable resin composition.
The content of the dye in the colorant (A) is usually 1% by mass or more in 100% by mass of the colorant (A), and is preferably 3% by mass or more, more preferably 5% by mass or more, from the viewpoint of increasing lightness. It is. The content of the dye may be 100% by mass in 100% by mass of the colorant (A).
The content of the xanthene dye in the dye is usually 5% by mass or more, preferably 8% by mass or more, in 100% by mass of the dye. The content of the xanthene dye may be 100% by mass in 100% by mass of the dye.
When the colorant (A) contains a pigment, the mass ratio of the dye content to the pigment content (dye content / pigment content) is usually 1/99 to 99/1, increasing the lightness. From the viewpoint, it is preferably 3/97 to 99/1, more preferably 3/97 to 70/30.

[2] Resin (B)
The colored curable resin composition of the present invention contains one or more resins (B). The resin (B) is preferably an alkali-soluble resin. Alkali-soluble refers to the property of being dissolved in a developer which is an aqueous solution of an alkali compound. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: At least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as “(a)”). ] And a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b)”. ) And a copolymer.
Resin [K2]: (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) [hereinafter referred to as “(c)” There is. ] And a copolymer.
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.

Specifically, as (a),
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, o-, m-, 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, 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 [2.2.1] bicyclounsaturated compounds containing a carboxy group such as 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 (hymic acid 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]. ;
Examples thereof include unsaturated (meth) acrylic acid containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) (meth) acrylic acid.
Especially, it is preferable that (a) is (meth) acrylic acid, maleic anhydride, etc. from a viewpoint of copolymerization reactivity or a solubility viewpoint to aqueous alkali solution.

  In the present specification, “(meth) acryl” represents at least one selected from the group consisting of acryl and methacryl. The same applies to notations such as “(meth) acryloyl” and “(meth) acrylate”.

(B) is a polymerization having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Refers to a chemical compound. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
(B) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter, referred to as “(b1)”. ], A monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b2)”. ] A monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as “(b3)”. ] Etc. are mentioned.

  (B1) is a monomer (b1-1) having a structure obtained by epoxidizing an unsaturated aliphatic hydrocarbon [hereinafter referred to as “(b1-1)”. ] Monomer (b1-2) having a structure obtained by epoxidizing unsaturated alicyclic hydrocarbon [hereinafter, 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.), a compound represented by the formula (I) And compounds represented by the formula (II).

[In Formula (I) and Formula (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted. X ¹ and ^{X 2} are each independently a single ^{bond, * - R c -, *} - R c -O -, * - R c -S-, or ^* represents a -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, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.
Examples of the alkanediyl group constituting R ^c include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5- Examples thereof include a diyl group and a hexane-1,6-diyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— (* represents a bond to O) group, or * —CH ₂ CH ₂ —O— group. More preferably a single bond or a * —CH ₂ CH ₂ —O— group.
Specific examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15), preferably the formula (I-1) and the formula (I-3). ), Formula (I-5), formula (I-7), formula (I-9), and compounds represented by formula (I-11) to formula (I-15), and more preferably Examples thereof include compounds represented by I-1), formula (I-7), formula (I-9), and formula (I-15).

  Specific examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15), preferably the formula (II-1) and the formula (II- 3), formula (II-5), formula (II-7), formula (II-9), compounds represented by formula (II-11) to formula (II-15), and more preferably formula Examples include compounds represented by (II-1), formula (II-7), formula (II-9), and formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. They can be mixed in any ratio. In the case of mixing, the mixing ratio is the formula (I): formula (II) [molar ratio], preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, still more preferably 20: 80-80: 20.
The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Preferred examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, 3-methyl-3- (meth) acryloyloxyethyl oxetane, 3-ethyl-3- (meth) acryloyloxyethyl oxetane is mentioned.
The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Preferred examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As a specific example of (c),
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, Lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8- Ile (meth) acrylate [in this technical field, it is called "dicyclopentanyl (meth) acrylate" as a common name. It may also be called “tricyclodecyl (meth) acrylate”. ], Tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate [in this technical field, it is called "dicyclopentenyl (meth) acrylate" as a common name. ], Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meth) acrylic acid esters such as (meth) acrylates;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. 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.
Among these, from the viewpoint of copolymerization reactivity and heat resistance, (c) includes benzyl (meth) acrylate, tricyclodecyl (meth) acrylate, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, Bicyclo [2.2.1] hept-2-ene and the like are preferable. Moreover, since it is excellent in the developability at the time of pattern formation, benzyl (meth) acrylate and tricyclodecyl (meth) acrylate are more preferable as (c).

In the resin [K1], the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the resin [K1].
A structural unit derived from (a); 2-50 mol% (more preferably 10-45 mol%),
A structural unit derived from (b), particularly a structural unit derived from (b1); 50 to 98 mol% (more preferably 55 to 90 mol%).
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability, developability, and solvent resistance of the resulting pattern tend to be excellent.
Resin [K1] is described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st edition, published on March 1, 1972) and the document. It can be produced with reference to the cited references.
Specifically, there is a method in which a predetermined amount of (a) and (b) (particularly (b1)), a polymerization initiator, a solvent, and the like are charged into a reaction vessel and stirred, heated, and kept warm in a deoxygenated atmosphere. Can be mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and any of those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide). It is done. The solvent is not particularly limited as long as it dissolves each monomer, and a solvent (E) described later can be used as a solvent for the colored curable resin composition.
As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each is preferably within the following range among all the structural units constituting the resin [K2].
A structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%),
A structural unit derived from (b), in particular a structural unit derived from (b1); 2-95 mol% (more preferably 5-80 mol%),
Structural unit derived from (c); 1 to 65 mol% (more preferably 5 to 60 mol%).
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability, developability, solvent resistance of the resulting pattern, heat resistance and mechanical strength tend to be excellent.
Resin [K2] can be produced in the same manner as described for the production method of resin [K1]. Specifically, a predetermined amount of (a), (b) (particularly (b1)) and (c), a polymerization initiator and a solvent are charged into a reaction vessel, and the mixture is stirred, heated and kept warm in a deoxygenated atmosphere. The method of doing is mentioned. As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used.

In the resin [K3], the ratio of the structural unit derived from each is preferably in the following range among all the structural units constituting the resin [K3].
A structural unit derived from (a); 2-55 mol% (more preferably 10-50 mol%),
Structural unit derived from (c); 45 to 98 mol% (more preferably 50 to 90 mol%).
Resin [K3] can be produced in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (b) has an oxirane ring of (b1) having a C2-C4 cyclic ether structure (b). It can manufacture by adding to the carboxylic acid and / or carboxylic anhydride which it has. Specifically, first, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from each is preferably in the following range among all the structural units constituting the copolymer of (a) and (c).
A structural unit derived from (a); 5-50 mol% (more preferably 10-45 mol%),
Structural unit derived from (c); 50 to 95 mol% (more preferably 55 to 90 mol%).

Next, a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer has a C2-C4 cyclic ether structure (b1), particularly (b1). React the oxirane ring. Specifically, following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with nitrogen to air, and (b) (particularly (b1)), carboxylic acid or carboxylic anhydride A reaction catalyst (such as tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (such as hydroquinone) in a flask and reaction at 60 to 130 ° C. for 1 to 10 hours. Resin [K4] can be obtained.
The amount of (b) used, in particular (b1), is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and sensitivity to become favorable. Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in the resin [K4], and (b1-1) is more preferable.
It is preferable that the usage-amount of the said reaction catalyst is 0.001-5 mass% with respect to the total amount of (a), (b) (especially (b1)) and (c). It is preferable that the usage-amount of the said polymerization inhibitor is 0.001-5 mass% with respect to 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) (particularly (b1)) and (c) 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) (particularly (b1)) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
A structural unit derived from (b), in particular a structural unit derived from (b1); 5-95 mol% (more preferably 10-90 mol%),
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%).

  Furthermore, under the same conditions as in the production method of the resin [K4], the cyclic ether structure derived from (b) of the copolymer of (b) (particularly (b1)) and (c), The resin [K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride having the resin. The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b) (particularly (b1)). Since the reactivity of the cyclic ether structure is high and unreacted (b) hardly remains, (b1) is preferable as (b) used in 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 the hydroxy group generated by the reaction of the cyclic ether structure 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.

  Of the resins [K1] to [K6], a preferable resin as the resin (B) is [K1] or [K2]. Resin (B) may consist of 1 type of resin, and may contain 2 or more types of resin.

The polystyrene equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. 000. When the weight average molecular weight (Mw) is in the above range, the solubility of the unexposed area in the developer is high, and the residual film ratio and hardness of the resulting pattern tend to be high. 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 solution acid value of the resin (B) is preferably 5 to 180 mg-KOH / g, more preferably 10 to 100 mg-KOH / g, and further preferably 12 to 50 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined, for example, by titrating with an aqueous potassium hydroxide solution.
The content of the resin (B) is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and further preferably 15 to 40% in a solid content of 100% by mass of the colored curable resin composition. % By mass. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

[3] Polymerizable compound (C)
The polymerizable compound (C) is not particularly limited as long as it is a compound that can be polymerized by an active radical generated from the polymerization initiator (D) by light irradiation or the like, and a compound having a polymerizable ethylenically unsaturated bond, etc. Is mentioned. The weight average molecular weight of the polymerizable compound (C) is preferably 3,000 or less.
Among them, the polymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds, such as 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 te La (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 And caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable.
The colored curable resin composition of the present invention can contain one or more polymerizable compounds (C). The content of the polymerizable compound (C) is preferably 20 to 150 parts by mass, more preferably 80 to 120 parts by mass with respect to 100 parts by mass of the resin (B) in the colored curable resin composition. .

[4] Polymerization initiator (D)
The colored curable resin composition of the present invention contains one or more polymerization initiators (D). The polymerization initiator (D) is a compound that can generate an active radical, an acid, or the like by the action of light or heat to initiate polymerization.
In the colored curable resin composition of the present invention, the polymerization initiator (D) includes a polymerization initiator (photopolymerization initiator) represented by the formula (D-1). The colored curable resin composition can contain one or more polymerization initiators as the polymerization initiator (D-1).

[Wherein, R ^d1 and R ^d2 each independently represent a hydrogen atom, a chain alkyl group which may have a substituent, or a cyclic organic group which may have a substituent, and R ^d1 And R ^d2 together may form a ring,
R ^d3 represents a monovalent organic group,
R ^d4 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group;
dm represents 0 or 1. ]

R ^d1 and R ^d2 each independently represent a hydrogen atom, a chain alkyl group which may have a substituent, or a cyclic organic group which may have a substituent, and R ^d1 and R ^d2 , Together may form a ring. R ^d1 and R ^d2 are preferably a chain alkyl group which may have a substituent.
In R ^d1 and R ^d2 , the chain alkyl group may be a linear alkyl group or a branched alkyl group.
When R ^d1 and R ^d2 are chain alkyl groups having no substituent, the chain alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms.
In R ^d1 and R ^d2 , the chain alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group. , Isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, An n-decyl group, an isodecyl group, etc. are mentioned.
When R ^d1 and R ^d2 are alkyl groups, the alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

When R ^d1 and R ^d2 are chain alkyl groups having a substituent, the carbon number of the chain alkyl group is preferably 1-20, more preferably 1-10, and still more preferably 1-6. This carbon number does not include the carbon number of the substituent. The chain alkyl group having a substituent is preferably linear.
Examples of the substituent include a cyano group, a halogen atom, a cyclic organic group, and an alkoxycarbonyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In these, a fluorine atom, a chlorine atom, and a bromine atom are preferable.
Examples of the cyclic organic group include a cycloalkyl group, an aromatic hydrocarbon group, and a heterocyclyl group.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.
The heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and O, or a heterocyclyl group in which such monocycles or such monocycles and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group.
The heterocyclic ring constituting the heterocyclyl group includes furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, iso Examples include indole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. .
When R ^d1 is an alkoxycarbonyl group, the alkoxy group contained in the alkoxycarbonyl group may be linear or branched, and is preferably linear. Carbon number of the alkoxy group contained in alkoxycarbonyl group becomes like this. Preferably it is 1-10, More preferably, it is 1-6.
When the chain alkyl group has a substituent, the number of substituents is not particularly limited, and is typically 1 to 20, preferably 1 to 10, more preferably 1 to 6.

When R ^d1 and R ^d2 are cyclic organic groups, the cyclic organic group may be an alicyclic group or an aromatic group.
Examples of the cyclic organic group include an aliphatic cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclyl group. The substituent that the cyclic organic group may have is the same as the substituent that the chain alkyl group may have.
The aliphatic cyclic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms of the aliphatic cyclic hydrocarbon group is not particularly limited, and is preferably 3 to 20, more preferably 3 to 10.
Examples of the monocyclic cyclic hydrocarbon group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, tricyclononyl group, tricyclodecyl group, tetracyclo group. A dodecyl group, an adamantyl group, etc. are mentioned.
The aromatic hydrocarbon group is a phenyl group, a group formed by bonding a plurality of benzene rings via a carbon-carbon bond, or a group formed by condensing a plurality of benzene rings. Preferably there is. When the aromatic hydrocarbon group is a phenyl group or a group formed by combining or condensing a plurality of benzene rings, the number of benzene rings contained in the aromatic hydrocarbon group is not particularly limited, Preferably it is 3 or less, More preferably, it is 2 or less, More preferably, it is 1.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a biphenylyl group, an anthryl group, and a phenanthryl group.
The heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, and O, or a heterocyclyl group in which such monocycles or such monocycles and a benzene ring are condensed. When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group.
The heterocyclic ring constituting the heterocyclyl group includes furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, iso Examples include indole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. .

R ^d1 and R ^d2 may be combined to form a ring. The group formed by the ring formed by R ^d1 and R ^d2 is preferably a cycloalkylidene group. The ring constituting the cycloalkylidene group is preferably a 5-membered ring to a 6-membered ring, more preferably a 5-membered ring.
The cycloalkylidene group may be condensed with one or more other rings. Rings that may be condensed with a cycloalkylidene group include benzene ring, naphthalene ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, furan ring, thiophene ring, pyrrole ring, pyridine ring, Examples include a pyrazine ring and a pyrimidine ring.

Preferable examples of R ^d1 and R ^d2 include groups represented by the formula -A ^d1 -A ^d2 . In the formula, A ^d1 is a linear alkylene group, and A ^d2 is an alkoxy group, a cyano group, a halogen atom, a halogenated alkyl group, a cyclic organic group, or an alkoxycarbonyl group.
The carbon number of the linear alkylene group of A ^d1 is preferably 1 to 10, more preferably 1 to 6.
When ^Ad2 is an alkoxy group, the alkoxy group may be linear or branched, and preferably linear. Carbon number of an alkoxy group becomes like this. Preferably it is 1-10, More preferably, it is 1-6.
When ^Ad2 is a halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable, and a fluorine atom, a chlorine atom and a bromine atom are more preferable.
When ^Ad2 is a halogenated alkyl group, the halogen atom contained in the halogenated alkyl group is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and more preferably a fluorine atom, a chlorine atom, or a bromine atom. The halogenated alkyl group may be linear or branched, and is preferably linear.
When A ^d2 is a cyclic organic group, examples of the cyclic organic group are the same as the cyclic organic group that R ^d1 and R ^d2 may have as a substituent.
When A ^d2 is an alkoxycarbonyl group, examples of the alkoxycarbonyl group are the same as the alkoxycarbonyl groups that R ^d1 and R ^d2 may have as a substituent.

Preferred examples of R ^d1 and R ^d2 include
Alkyl groups such as ethyl, n-propyl, n-butyl, n-hexyl, n-heptyl, and n-octyl;
2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, 5-methoxy-n-pentyl group, 6-methoxy-n-hexyl group, 7-methoxy-n-heptyl group 8-methoxy-n-octyl group, 2-ethoxyethyl group, 3-ethoxy-n-propyl group, 4-ethoxy-n-butyl group, 5-ethoxy-n-pentyl group, 6-ethoxy-n-hexyl Groups, alkoxyalkyl groups such as 7-ethoxy-n-heptyl group and 8-ethoxy-n-octyl group;
2-cyanoethyl group, 3-cyano-n-propyl group, 4-cyano-n-butyl group, 5-cyano-n-pentyl group, 6-cyano-n-hexyl group, 7-cyano-n-heptyl group, And a cyanoalkyl group such as 8-cyano-n-octyl group;
2-phenylethyl group, 3-phenyl-n-propyl group, 4-phenyl-n-butyl group, 5-phenyl-n-pentyl group, 6-phenyl-n-hexyl group, 7-phenyl-n-heptyl group And phenylalkyl groups such as 8-phenyl-n-octyl group;
2-cyclohexylethyl group, 3-cyclohexyl-n-propyl group, 4-cyclohexyl-n-butyl group, 5-cyclohexyl-n-pentyl group, 6-cyclohexyl-n-hexyl group, 7-cyclohexyl-n-heptyl group 8-cyclohexyl-n-octyl group, 2-cyclopentylethyl group, 3-cyclopentyl-n-propyl group, 4-cyclopentyl-n-butyl group, 5-cyclopentyl-n-pentyl group, 6-cyclopentyl-n-hexyl group A cycloalkylalkyl group such as a group, 7-cyclopentyl-n-heptyl group, and 8-cyclopentyl-n-octyl group;
2-methoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group, 4-methoxycarbonyl-n-butyl group, 5-methoxycarbonyl-n-pentyl group, 6-methoxycarbonyl-n-hexyl group, 7-methoxy Carbonyl-n-heptyl group, 8-methoxycarbonyl-n-octyl group, 2-ethoxycarbonylethyl group, 3-ethoxycarbonyl-n-propyl group, 4-ethoxycarbonyl-n-butyl group, 5-ethoxycarbonyl-n Alkoxycarbonylalkyl groups such as -pentyl, 6-ethoxycarbonyl-n-hexyl, 7-ethoxycarbonyl-n-heptyl and 8-ethoxycarbonyl-n-octyl;
2-chloroethyl group, 3-chloro-n-propyl group, 4-chloro-n-butyl group, 5-chloro-n-pentyl group, 6-chloro-n-hexyl group, 7-chloro-n-heptyl group, 8-chloro-n-octyl group, 2-bromoethyl group, 3-bromo-n-propyl group, 4-bromo-n-butyl group, 5-bromo-n-pentyl group, 6-bromo-n-hexyl group, 7-bromo-n-heptyl group, 8-bromo-n-octyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro-n-pentyl And halogenated alkyl groups such as groups.

More preferable examples of R ^d1 and R ^d2 include an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, a 2-methoxyethyl group, a 2-cyanoethyl group, a 2-phenylethyl group, and 2-cyclohexyl. Ethyl group, 2-methoxycarbonylethyl group, 2-chloroethyl group, 2-bromoethyl group, 3,3,3-trifluoropropyl group, and 3,3,4,4,5,5,5-heptafluoro-n -A pentyl group etc. are mentioned.

Examples of suitable organic groups for R ^d3 include alkyl groups, alkoxy groups, cycloalkyl groups, cycloalkoxy groups, saturated aliphatic acyl groups, alkoxycarbonyl groups, saturated aliphatic acyloxy groups, and substituents. Good phenyl group, optionally substituted phenoxy group, optionally substituted benzoyl group, optionally substituted phenoxycarbonyl group, optionally substituted Benzoyloxy group, phenylalkyl group optionally having substituent, naphthyl group optionally having substituent, naphthoxy group optionally having substituent, and optionally having substituent A naphthoyl group, an optionally substituted naphthoxycarbonyl group, an optionally substituted naphthoyloxy group, an optionally substituted naphthylalkyl group, An optionally substituted heterocyclyl group, an optionally substituted heterocyclylcarbonyl group, an amino group substituted with 1 or 2 organic groups, a morpholin-1-yl group, and piperazine-1- Yl group, cycloalkylalkyl group, phenoxyalkyl group which may have a substituent on the aromatic ring, phenylthioalkyl group which may have a substituent on the aromatic ring, and the like.

In ^Rd3 , the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. The alkyl group may be linear or branched.
As the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, etc. Is mentioned.
The alkyl group may contain an ether bond (—O—) in the carbon chain. Examples of the alkyl group having an ether bond in the carbon chain include a methoxyethyl group, an ethoxyethyl group, a methoxyethoxyethyl group, an ethoxyethoxyethyl group, a propyloxyethoxyethyl group, and a methoxypropyl group.

In R ^d3 , the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. The alkoxy group may be linear or branched.
As an alkoxy group, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, isobutyloxy group, sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, isopentyloxy group , Sec-pentyloxy group, tert-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, isooctyloxy group, sec-octoxyl group, tert-octyloxy group, n-nonyloxy group Group, isononyloxy group, n-decyloxy group, isodecyloxy group and the like.
The alkoxy group may contain an ether bond (—O—) in the carbon chain. Examples of the alkoxy group having an ether bond in the carbon chain include a methoxyethoxy group, an ethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, a propyloxyethoxyethoxy group, and a methoxypropyloxy group.

In R ^d3 , the cycloalkyl group or cycloalkoxy group preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms.
Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Examples of the cycloalkoxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, and a cyclooctyloxy group.

In R ^d3 , the saturated aliphatic acyl group or the saturated aliphatic acyloxy group preferably has 2 to 21 carbon atoms, more preferably 2 to 7 carbon atoms.
As saturated aliphatic acyl groups, acetyl group, propanoyl group, n-butanoyl group, 2-methylpropanoyl group, n-pentanoyl group, 2,2-dimethylpropanoyl group, n-hexanoyl group, n-heptanoyl group, n-octanoyl group, n-nonanoyl group, n-decanoyl group, n-undecanoyl group, n-dodecanoyl group, n-tridecanoyl group, n-tetradecanoyl group, n-pentadecanoyl group, and n-hexadecanoyl group Groups and the like.
The saturated aliphatic acyloxy group includes acetyloxy group, propanoyloxy group, n-butanoyloxy group, 2-methylpropanoyloxy group, n-pentanoyloxy group, 2,2-dimethylpropanoyloxy group, n -Hexanoyloxy group, n-heptanoyloxy group, n-octanoyloxy group, n-nonanoyloxy group, n-decanoyloxy group, n-undecanoyloxy group, n-dodecanoyloxy group, n-tri Examples include decanoyloxy group, n-tetradecanoyloxy group, n-pentadecanoyloxy group, and n-hexadecanoyloxy group.

In R ^d3 , the carbon number of the alkoxycarbonyl group is preferably 2 to 20, more preferably 2 to 7.
Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, isopropyloxycarbonyl group, n-butyloxycarbonyl group, isobutyloxycarbonyl group, sec-butyloxycarbonyl group, tert-butyloxycarbonyl Group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl group, tert-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, Isooctyloxycarbonyl group, sec-octyloxycarbonyl group, tert-octyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl , N- decyloxy group, and the like isodecyl oxycarbonyl group.

In R ^d3 , the phenylalkyl group preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms.
In R ^d3 , the naphthylalkyl group preferably has 11 to 20 carbon atoms, more preferably 11 to 14 carbon atoms.
Examples of the phenylalkyl group include a benzyl group, a 2-phenylethyl group, a 3-phenylpropyl group, and a 4-phenylbutyl group.
Examples of the naphthylalkyl group include an α-naphthylmethyl group, a β-naphthylmethyl group, a 2- (α-naphthyl) ethyl group, and a 2- (β-naphthyl) ethyl group.
When R ^d3 is a phenylalkyl group or a naphthylalkyl group, R ^d3 may further have a substituent on the phenyl group or naphthyl group.

In R ^d3 , the heterocyclyl group is a 5- or 6-membered monocycle containing one or more N, S, or O, or a heterocyclyl group in which such monocycles or such monocycles and a benzene ring are condensed. . When the heterocyclyl group is a condensed ring, the number of condensed rings is 3 or less. The heterocyclyl group may be an aromatic group (heteroaryl group) or a non-aromatic group.
The heterocyclic ring constituting the heterocyclyl group includes furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, thiadiazole, isothiazole, imidazole, pyrazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, benzofuran, benzothiophene, indole, iso Examples include indole, indolizine, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, quinoline, isoquinoline, quinazoline, phthalazine, cinnoline, quinoxaline, piperidine, piperazine, morpholine, piperidine, tetrahydropyran, and tetrahydrofuran. .
The heterocyclyl group may further have a substituent.

In R ^d3 , the heterocyclyl group contained in the heterocyclylcarbonyl group is the same as in the case where R ^d3 is a heterocyclyl group.
The heterocyclylcarbonyl group may further have a substituent.

In R ^d3 , the organic group that the amino group substituted with 1 or 2 organic groups may have is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an alkyl group having 2 to 21 carbon atoms. Saturated aliphatic acyl group, phenyl group optionally having substituent, benzoyl group optionally having substituent, phenylalkyl group having 7 to 20 carbon atoms optionally having substituent, substituted Examples thereof include a naphthyl group which may have a group, a naphthoyl group which may have a substituent, a naphthylalkyl group having 11 to 20 carbon atoms which may have a substituent, and a heterocyclyl group.
Specific examples of the amino group substituted with one or two organic groups include methylamino group, ethylamino group, diethylamino group, n-propylamino group, di-n-propylamino group, isopropylamino group, and n-butyl. Amino group, di-n-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, n-nonylamino group, n-decylamino group, phenylamino group, naphthyl Amino group, acetylamino group, propanoylamino group, n-butanoylamino group, n-pentanoylamino group, n-hexanoylamino group, n-heptanoylamino group, n-octanoylamino group, n-deca Examples thereof include a noylamino group, a benzoylamino group, an α-naphthoylamino group, and a β-naphthoylamino group.

^Examples of the substituent in the case where the phenyl group, naphthyl group, and heterocyclyl group included in R ^d3 further have a substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and 2 to 2 carbon atoms. A saturated aliphatic acyl group having 7 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms, a saturated aliphatic acyloxy group having 2 to 7 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms And a dialkylamino group having an alkyl group, a morpholin-1-yl group, a piperazin-1-yl group, a halogen, a nitro group, and a cyano group.
When the phenyl group, naphthyl group, and heterocyclyl group contained in R ^d3 further have a substituent, the number of the substituent is preferably 1 to 4. When it has a plurality of substituents, the plurality of substituents may be the same or different.

R ^d3 is preferably an alkyl group, a cycloalkyl group, a phenyl group which may have a substituent, a cycloalkylalkyl group, or a phenylthioalkyl group which may have a substituent on the aromatic ring.
As an alkyl group, a C1-C20 alkyl group is preferable, a C1-C8 alkyl group is more preferable, a C1-C4 alkyl group is more preferable, and a methyl group is the most preferable.
Among the phenyl groups that may have a substituent, a methylphenyl group is preferable, and a 2-methylphenyl group is more preferable.
Carbon number of the cycloalkyl group contained in the cycloalkylalkyl group is preferably 5 to 10, more preferably 5 to 8, and further preferably 5 or 6. Carbon number of the alkylene group contained in a cycloalkylalkyl group becomes like this. Preferably it is 1-8, More preferably, it is 1-4, More preferably, it is 2. Of the cycloalkylalkyl groups, a cyclopentylethyl group is preferred.
Carbon number of the alkylene group contained in the phenylthioalkyl group which may have a substituent on an aromatic ring becomes like this. Preferably it is 1-8, More preferably, it is 1-4, More preferably, it is 2. Among the phenylthioalkyl groups which may have a substituent on the aromatic ring, a 2- (4-chlorophenylthio) ethyl group is preferable.

As R ^d3 , a group represented by —A ^d3 —CO—O—A ^d4 is also preferable. ^Ad3 is a divalent organic group, preferably a divalent hydrocarbon group, more preferably an alkylene group. A ^d4 is a monovalent organic group, and is preferably a monovalent hydrocarbon group.
In ^Ad3 , the alkylene group may be linear or branched, and is preferably linear. Carbon number of an alkylene group becomes like this. Preferably it is 1-10, More preferably, it is 1-6, More preferably, it is 1-4.
The A ^d4, alkyl group having 1 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Preferable examples of ^{Ad 4} include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and n-hexyl group. , Phenyl group, naphthyl group, benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group and the like.

Preferable examples of the group represented by -A ^d3 -CO-O-A ^d4 include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propyloxycarbonylethyl group, 2-n- Butyloxycarbonylethyl group, 2-n-pentyloxycarbonylethyl group, 2-n-hexyloxycarbonylethyl group, 2-benzyloxycarbonylethyl group, 2-phenoxycarbonylethyl group, 3-methoxycarbonyl-n-propyl group 3-ethoxycarbonyl-n-propyl group, 3-n-propyloxycarbonyl-n-propyl group, 3-n-butyloxycarbonyl-n-propyl group, 3-n-pentyloxycarbonyl-n-propyl group, 3-n-hexyloxycarbonyl-n-propyl group, 3-benzyloxycarbonyl -n- propyl group, and 3-phenoxycarbonyl -n- propyl group and the like.

R ^d3 is preferably a group represented by the formula (R3-a) or (R3-b). * Represents a bond.

[In Formula (R3-a) and Formula (R3-b), R ^d5 and R ^d6 each independently represent an organic group, p represents an integer of 0 to 4, and R ^d5 and R ^d6 represent a benzene ring. R ^d5 and R ^d6 together may form a ring when present at adjacent positions above, q represents an integer of 1-8, r represents an integer of 1-5, s Represents an integer of 0 to (r + 3), and R ^d7 represents an organic group. ]

In R ^d5 and R ^d6 , examples of the organic group are the same as those of the preferable organic group of R ^d3 . R ^d5 is preferably an alkyl group or a phenyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and most preferably 1.
When R ^d5 and R ^d6 together form a ring, the ring may be an aromatic ring or an aliphatic ring. Examples of the group represented by the formula (R3-a) in which R ^d5 and R ^d6 form a ring include naphthalen-1-yl group, 1,2,3,4-tetrahydro And naphthalen-5-yl group.
p is preferably 0 or 1, more preferably 0.

In R ^d7 , examples of the organic group are the same as those of the preferable organic group of R ^d3 . R ^d7 is preferably an alkyl group. The alkyl group may be linear or branched. Carbon number of an alkyl group becomes like this. Preferably it is 1-10, More preferably, it is 1-5, More preferably, it is 1-3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, and a methyl group is preferable.
q is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
r is preferably an integer of 1 to 3, and more preferably 1 or 2.
s is preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0.

R ^{d4 in} formula (D-1) is a hydrogen atom, an alkyl group having 1 to 11 carbon atoms that may have a substituent, or an aryl group that may have a substituent.
Examples of the substituent that the alkyl group may have include a phenyl group and a naphthyl group.
Examples of the substituent that the aryl group may have include an alkyl group having 1 to 5 carbon atoms, an alkoxy group, and a halogen atom.
R ^d4 is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a phenyl group, a benzyl group, a methylphenyl group, a naphthyl group, and more preferably a methyl group. Group or phenyl group.

  Dm in the formula (D-1) is an integer of 0 or 1. Dm is preferably 1 from the viewpoint of forming a colored cured coating film having a good film thickness retention.

The polymerization initiator represented by the formula (D-1) represents an oxime group (= N—OH) contained in the compound represented by the formula (D-1a) by ═N—O—COR ^d4. It can be produced by a method including a step of converting to an oxime ester group. R ^d4 has the same meaning as R ^d4 in formula (D-1).

Wherein ^{(D-1a), R d1} , R d2, R d3, and dm are the same meaning as ^{R d1, R d2, R d3} , and dm in the formula (D-1). ]

As a method of converting an oxime group (= N—OH) into an oxime ester group represented by ═N—O—COR ^d4 , an acyl which gives an acyl group represented by —COR ^{d4 to} a hydroxyl group in the oxime group is used. The method of making an agent react is mentioned. Examples of the acylating agent include an acid anhydride represented by (R ^d4 CO) ₂ O and an acid halide represented by R ^d4 COX (X is a halogen atom).

When dm is 0, the compound represented by the formula (D-1a) is obtained by using an acid halide, an acid anhydride, or the like for the fluorene compound substituted at the 9-position with R ^d1 or R ^d2 , and —CO—. introducing an acyl group represented by R ^d3, the introduced acyl group, with hydroxylamine or the like, comprising the step of converting the group represented by -C (= N-OH) -R d3 Can be manufactured by.

When the compound represented by the formula (D-1a) has a dm of 1, a 9-position substituted fluorene compound substituted with R ^d1 and R ^d2 by using an acid halide or the like, —CO—CH ₂ —R It can be produced by a method including a step of introducing an acyl group represented by ^d3 and a step of oximation of a methylene group of the introduced acyl group using a nitrite or the like.

Preferable examples of the compound represented by the formula (D-1) and dm being 1 include compounds in which R ^d1 , R ^d2 , R ^d3 and R ^d4 are groups described in Table 1 (D-1- 1) to (D-1-25).

The polymerization initiator (D) can contain other polymerization initiators other than the polymerization initiator represented by the formula (D-1).
As other polymerization initiators, known polymerization initiators can be used.
Other polymerization initiators include oxime compounds such as O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds, benzoin compounds, benzophenone compounds, quinone compounds, 10-butyl-2- Examples include chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
The colored curable resin composition can contain one or more polymerization initiators as other polymerization initiators.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 25 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part, More preferably, it is 5-20 mass parts.

  From the viewpoint of forming a colored cured coating film having a good film thickness retention, the content of the polymerization initiator represented by the formula (D-1) in the polymerization initiator (D) is preferably 50% by mass or more. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more, Still more preferably, it is 95 mass% or more, Most preferably, it is 100 mass%.

[5] Polymerization initiation assistant (D1)
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Of these, thioxanthone compounds are preferred. Two or more polymerization initiation assistants (D1) may be used in combination.

  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, among which 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 phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

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

[6] Solvent (E)
The colored curable resin composition of the present invention preferably contains a solvent (E). The colored curable resin composition can contain one or more solvents as the solvent (E). As the solvent (E), ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), Examples include ketone solvents (solvents containing —CO—) other than ester solvents, alcohol solvents, aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

  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, include phenetol and methyl anisole and the like.

  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, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate and the like.

  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.

  It is preferable that a solvent (E) contains the organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less from the point of applicability | paintability and drying property. Among them, the solvent (E) is 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, 3-methoxybutyl acetate, 3 It preferably contains at least one selected from the group consisting of -methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N, N-dimethylformamide, propylene glycol monomethyl ether acetate, propylene glycol monomethyl Ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1- More preferably contains at least one selected from methanol and the group consisting of ethyl 3-ethoxypropionate.

  The content of the solvent (E) in the colored curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass. In other words, 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 in the above range, the flatness at the time of coating is good, and the color density does not become insufficient when a color filter is formed, so that the display characteristics tend to be good.

[7] Leveling agent (F)
The colored curable resin composition of the present invention can contain a leveling agent (F). The colored curable resin composition can contain one or more leveling agents as the leveling agent (F). Examples of the leveling agent (F) include a silicone surfactant (having no fluorine atom), a fluorine surfactant, a silicone surfactant having a fluorine atom, and the like. 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 a surfactant 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 a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  The content of the leveling agent (F) is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less in the colored curable resin composition. Preferably they are 0.005 mass% or more and 0.05 mass% or less. This content does not include the content of the pigment dispersant.

[8] Antioxidant (G)
From the viewpoint of improving the heat resistance and light resistance of the colorant (A), the colored curable resin composition preferably contains an antioxidant. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used. Two or more antioxidants may be used.

  Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1076. (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corp.), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ″, 5 , 5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corp.), Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-ter -Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corporation), Irganox 3790 (Irganox 3790: 1,3) 5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, BASF (strain ), Irganox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corp.), Irganox 1135 (Irganox 1135: Benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester , Manufactured by BASF), Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125 (Irganox 3125, manufactured by BASF) ), Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine, BASF (strain) ), Adekastab AO-80 (Adekastab AO-80: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl Ethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA Corporation), Milliser BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumiser G-80 (Sumizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumiser GS (Sumizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox) 1790, manufactured by Cytec Co., Ltd.) and vitamin E (manufactured by Eisai Co., Ltd.).

  Examples of phosphorus antioxidants include Irgafos 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Corp.), Irgafos 12 (Irgafos 12: Tris [2-[[2 , 4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (manufactured by BASF Corp.), Irgaphos 38 ( Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corporation), Adeka Stub 329K (manufactured by ADEKA Corporation), Adeka Stub PEP36 ( (Manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab PE Q (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (manufactured by Ultranox 626, manufactured by GE), and Sumitizer GP: 6- [ 3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphine Pin) (manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of sulfur-based antioxidants include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Is mentioned.

[9] Other components The colored curable resin composition of the present invention includes, as necessary, a filler, a polymer compound other than the resin (B), an adhesion promoter, an ultraviolet absorber, an aggregation inhibitor, an organic acid. In addition, one or more additives such as an organic amine compound, a thiol compound, and a curing agent can be contained.

  Examples of the filler include glass, silica, and alumina. Examples of the polymer compound other than the resin (B) include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples include silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of ultraviolet absorbers include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole; benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone Compound; benzoate compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2- (4,6-diphenyl-1,3,5-triazine- 2-yl) -5-hexyloxyphenol and other triazine compounds; Examples of the aggregation inhibitor include sodium polyacrylate.

Organic acids are used to adjust developability. Specifically,
Aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid;
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
And aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, and pyromellitic acid.

As an organic amine compound,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine Monoalkylamines such as n-undecylamine and n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di- dialkylamines such as n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol ;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Aminoalkane diols such as 2, 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol, 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanol such as 1-aminocyclopentanone methanol, 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanol such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, aminobenzoic acid such as p-diethylaminobenzoic acid; and the like.

  Examples of the curing agent include a compound that can react with the carboxy group in the resin (B) when heated to crosslink the resin (B), a compound that can be polymerized alone to cure the colored pattern, and the like. , Epoxy compounds, oxetane compounds and the like. Only 1 type may be used for a hardening | curing agent and it may use 2 or more types together.

  Epoxy compounds include bisphenol A epoxy resins, hydrogenated bisphenol A epoxy resins, bisphenol F epoxy resins, hydrogenated bisphenol F epoxy resins, novolac epoxy resins, other aromatic epoxy resins, and alicyclic compounds. Epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, aliphatic resins other than epoxy resins and brominated derivatives thereof, fats Examples include cyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like. It is done. Examples of commercially available epoxy resins include orthocresol novolac type epoxy resins, “Sumiepoxy (registered trademark) ESCN-195XL-80” (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored curable resin composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. Good. Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

As polyvalent carboxylic acid,
Aromatic polyvalent carboxylic acids such as 3,4-dimethylphthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid acid;
Aliphatic polycarboxylic acids such as 1,2,3,4-butanetetracarboxylic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid Alicyclic polycarboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid; and the like.

As polyvalent carboxylic acid anhydride,
Aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride ;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride and nadic anhydride;
And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerol tristrimellitic anhydride.

  As the carboxylic acid anhydride, a commercially available epoxy resin curing agent may be used. As the epoxy resin curing agent, trade name “Adeka Hardener (registered trademark) EH-700” (manufactured by ADEKA), trade name “Rikacid (registered trademark) HH” (manufactured by Shin Nippon Rika), trade name "MH-700" (manufactured by Shin Nippon Rika Co., Ltd.)

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

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention comprises a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and, if necessary, a solvent (E), a leveling agent ( F), a polymerization initiation assistant (D1), an antioxidant (G), and other components can be mixed.

<Color filter and manufacturing method thereof, color filter and display device>
The colored curable resin composition of the present invention is useful as a material for a color filter. A color filter formed from the colored curable resin composition of the present invention also falls within the scope of the present invention. The color filter may form a colored pattern.
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an ink jet method, a printing method, and the like, and preferably a photolithographic method. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography 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. A colored pattern or a colored coating film formed from the colored curable resin composition of the present invention is the color filter of the present invention.

  As a substrate, glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the above substrate In addition, an aluminum, silver, silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The formation of each color pixel by the photolithography method can be performed by a known or commonly used apparatus or conditions, and can be manufactured as follows, for example. First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include spin coating, slit coating, and slit and spin coating.
As temperature in performing heat drying, 30-120 degreeC is preferable and 50-110 degreeC is more preferable. Further, the heating time is preferably 10 seconds to 5 minutes, more preferably 30 seconds to 3 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. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.
Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
The exposure can be performed by irradiating the entire exposed surface with parallel light rays or by accurately aligning the photomask with the substrate on which the colored composition layer is formed. It is preferred to use an apparatus.
A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline 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. After development, it is preferable to wash with water.
Furthermore, it is preferable to post-bake the obtained colored pattern. As post-baking temperature, 150-250 degreeC is preferable and 160-235 degreeC is more preferable. As post-baking time, 1-120 minutes are preferable and 10-60 minutes are more preferable.
Since the film thickness of the obtained colored coating film affects adjacent pixels, it is preferable that it is as thin as possible. In particular, when the film is thick, the light from the light source may leak through the pixels of two or more colors when the liquid crystal panel is manufactured. May be lost. The film thickness of the colored coating film after post-baking is generally preferably 3 μm or less, and more preferably 2.8 μm or less. Although the minimum of the film thickness of a colored coating film is not specifically limited, Usually, it is 1 micrometer or more and may be 1.5 micrometers or more.
The colored coating film is excellent as a color filter material because it can exhibit excellent developability.
The color filter according to the present invention is useful as a color filter used in display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

<Synthesis Example 1: Preparation of dye (A1)>
20 parts of the compound represented by the above formula (1a) and 200 parts of N-propyl-2,6-dimethylaniline (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light-shielding conditions, and the resulting solution was 110 ° C. For 6 hours.
The obtained reaction solution was cooled to room temperature, added to a mixed solution of 800 parts of water and 50 parts of 35 mass% hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were obtained as a suction filtration residue and then dried to obtain a compound represented by the above formula (1-24). Hereinafter, the compound is referred to as “dye (A1)”.

<Synthesis Example 2: Preparation of dye (A2)>
40.6 parts of the compound represented by the above formula (1a) and 8 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the presence of 50 parts of 1-methyl-2-pyrrolidone under light-shielding conditions, and 30 Stir at 0 ° C. for 3 hours. After cooling the obtained reaction mixture to room temperature, the reaction mixture was added to a mixed solution of 400 parts of water and 20 parts of 35% hydrochloric acid and stirred at room temperature for 1 hour, whereby crystals were deposited. The precipitated crystals were obtained as a suction filtration residue and then dried to obtain 44 parts of a compound represented by the formula (I-1-A).

  Next, 44 parts of the compound represented by the formula (I-1-A) and 21.4 parts of trimethoxy [3- (methylamino) propyl] silane (manufactured by Tokyo Chemical Industry Co., Ltd.) were combined with 1-methyl-2- The mixture was heated at 100 ° C. for 5 hours in the presence of 50 parts of pyrrolidone. The obtained reaction mixture was cooled to room temperature, filtered, washed with 100 parts of water, and the obtained crystals were dried to obtain 52 parts of a compound represented by the formula (I-1). Hereinafter, the compound is referred to as “dye (A2)”.

<Synthesis Example 3: Preparation of dye (A3)>
After flowing nitrogen into a flask equipped with a condenser and a stirrer to make a nitrogen atmosphere, 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide were added, The obtained mixed solution was ice-cooled. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, followed by stirring for 1 hour while raising the temperature to room temperature.
Next, 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction mixture was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, it stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of a compound represented by the formula (C-I-18).

  Nitrogen was passed through a flask equipped with a condenser and a stirrer to create a nitrogen atmosphere, and 8.2 parts of the compound represented by the formula (BI-7) and the compound represented by the formula (CI-18) After adding 10 parts and 20 parts of toluene, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170 parts of isopropanol. Next, the diluted reaction mixture was poured into 300 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Stirring was stopped and the mixture was allowed to stand for 30 minutes to separate into an organic layer and an aqueous layer. After the aqueous layer was removed by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of sodium sulfate was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The solvent was distilled off from the obtained organic layer to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18).

Nitrogen was allowed to flow through a flask equipped with a condenser and a stirrer to form a nitrogen atmosphere. After charging 8 parts of the compound represented by the formula (A-II-18) and 396 parts of methanol, the mixture was stirred at room temperature for 30 minutes. A blue solution was prepared. Subsequently, after adding 396 parts of water to this blue solution, the mixture was further stirred at room temperature for 30 minutes to obtain a reaction mixture.
53 parts of water was put into a beaker, and 11.8 parts of Keggin-type phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol were put into the water and mixed at room temperature in an air atmosphere. A solution was prepared. The obtained phosphotungstic acid solution was added dropwise to the previously prepared reaction mixture over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200 parts of water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of a compound represented by the formula (AI-18). Hereinafter, the compound is referred to as “dye (A3)”.

<Synthesis Example 4: Preparation of Dispersion (A3)>
Dye (A3) 10 parts Dispersant 2.0 parts Resin contained in resin solution (B2) [solid content conversion] 4.0 parts Propylene glycol monomethyl ether acetate 84 parts are mixed, and dye (A3) is mixed using a bead mill. By sufficiently dispersing, a dispersion liquid (A3) was obtained.
BYK (registered trademark) -LPN6919 (manufactured by Big Chemie Japan) was used as the dispersant.

<Synthesis Example 5: Preparation of dispersion (A4)>
Pigment (A1) 12.1 parts Acrylic pigment dispersant 3.9 parts 84 parts of propylene glycol monomethyl ether acetate was mixed and the pigment was sufficiently dispersed using a bead mill to obtain dispersion (A4).
The pigment (A1) is a compound represented by the following formula.

<Synthesis Example 6: Preparation of dispersion (A5)>
C. I. Pigment Blue 15: 6 12 parts Acrylic pigment dispersant 2.0 parts Propylene glycol monomethyl ether acetate 86 parts were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain a dispersion (A5).

<Synthesis Example 7: Preparation of resin solution (B1)>
Nitrogen was passed through a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 46 parts of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the above formula (I-1) and the above formula (II-1) A solution prepared by dissolving 240 parts of a 1: 1 mixture (molar ratio) with a compound represented by the following formula in 185 parts of ethyl lactate, and adding the solution to 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm.
On the other hand, a solution prepared by dissolving 30 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of dropping, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a resin solution (B1) having a solid content of 26% by mass and an acid value of 120 mg-KOH / g (solid content conversion). The weight average molecular weight (Mw) of the resin contained in the obtained resin solution (B1) was 9,100, and the molecular weight distribution was 2.1.
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions. The ratio (Mw / Mn) between the weight average molecular weight (Mw) in terms of polystyrene and the number average molecular weight (Mn) obtained under the following conditions was defined as the molecular weight distribution.

Apparatus; K2479 (manufactured by Shimadzu Corporation),
Column; SHIMADZU Shim-pack GPC-80M,
Column temperature; 40 ° C
Solvent; THF,
Flow rate: 1.0 mL / min,
Test liquid solid content concentration; 0.001 to 0.01% by mass,
Injection volume: 50 μL,
Detector; RI,
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation).

  The resin contained in the resin solution (B1) has the structural units shown below.

<Synthesis Example 8: Preparation of resin solution (B2)>
Nitrogen was allowed to flow into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. with stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (in the compound represented by the above formula (I-1) and the above formula (II-1) A solution was prepared by dissolving 225 parts of a 1: 1 mixture (molar ratio) with the compound represented and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate. Using a funnel, the solution was dropped into a flask kept at 85 ° C. over 4 hours.
On the other hand, a mixed solution in which 30 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 160 parts of propylene glycol monomethyl ether acetate was dropped into the flask using another dropping funnel over 5 hours. After completion of dropping, the mixture was kept at 85 ° C. for 4 hours, and then cooled to room temperature. ) The weight average molecular weight (Mw) of the resin contained in the obtained resin solution (B2) was 11,000, and the molecular weight distribution was 2.01. The measurement method of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin was the same as in Synthesis Example 7.

  The resin contained in the resin solution (B2) has the structural units shown below.

<Synthesis Example 9: Preparation of polymerization initiator (D1)>
Nitrogen was passed through a flask equipped with a stirrer to create a nitrogen atmosphere, and 10 parts of 9,9-di-n-propylfluorene, 7.4 parts of (2-methylphenyl) acetic chloride, and 160 parts of dichloromethane were added and mixed. did. Subsequently, the mixture in the flask was ice-cooled, 6.4 parts of aluminum chloride was added with stirring, and the mixture was reacted for 1 hour under ice-cooling. After completion of the reaction, the reaction mixture was poured into ice water and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off. The residue was purified by a silica gel column to give 2- (2-methylphenyl) acetyl-9,9-di-n-propylfluorene.
Next, nitrogen was passed through a flask equipped with a stirrer to form a nitrogen atmosphere, and 14.5 parts of 2- (2-methylphenyl) acetyl-9,9-di-n-propylfluorene, 3.9 parts of concentrated hydrochloric acid, And 60 parts of dimethylformamide were added and mixed. Next, the mixture in the flask was ice-cooled, and 5.9 parts of isobutyl nitrite was added with stirring, followed by reaction for 3 hours under ice-cooling. After completion of the reaction, the solvent was distilled off from the reaction mixture, ethyl acetate was added to the residue, washed with saturated brine, dried over anhydrous magnesium sulfate, the solvent was distilled off again, and 2- [ 2-Methylphenyl (hydroxyimino) acetyl] -9,9-di-n-propylfluorene was obtained.

  Next, nitrogen is passed through a flask equipped with a stirrer to form a nitrogen atmosphere, 10 parts of 2- [2-methylphenyl (hydroxyimino) acetyl] -9,9-di-n-propylfluorene, acetic anhydride 3.0. Part, 2.8 parts of triethylamine, and 90 parts of dimethylformamide were stirred and reacted at 35 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, ethyl acetate was added to the reaction mixture, washed with water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The residue was purified by a silica gel column to obtain a polymerization initiator (D1) having the following structure.

<Examples 1-3 and Comparative Example 1>
(1) Preparation of colored curable resin composition Dye (A1) or (A2) obtained in Synthesis Example 1 or 2, Dispersions (A3) to (A5) obtained in Synthesis Examples 4 to 6, and Synthesis Example Table 2 shows the resin solution (B1), the polymerizable compound (C1), the polymerization initiator (D1) or (D2), the solvents (E1) and (E2), and the leveling agent (F1) obtained in 7. It mixed so that it might become the compounding quantity of this, and the colored curable resin composition was obtained. The unit of the amount of each component in Table 2 is “parts by mass”. Details of each component are as follows.

[1] Dye (A1): Dye (A1) obtained in Synthesis Example 1
[2] Dye (A2): Dye (A2) obtained in Synthesis Example 2
[3] Dispersion (A3): Dispersion (A3) obtained in Synthesis Example 4
[4] Dispersion (A4): Dispersion (A4) obtained in Synthesis Example 5
[5] Dispersion (A5): Dispersion (A5) obtained in Synthesis Example 6
[6] Resin solution (B1): Resin solution (B1) obtained in Synthesis Example 7
[7] Polymerizable compound (C1): Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
[8] Polymerization initiator (D1): polymerization initiator (D1) obtained in Synthesis Example 8
[9] Polymerization initiator (D2): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF Corporation)
[10] Leveling agent (F1): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)
[11] Solvent (E1): Diacetone alcohol [12] Solvent (E2): Propylene glycol monomethyl ether acetate

(2) Evaluation of film thickness retention ratio A colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the substrate coated with the colored curable resin composition is exposed to 80 mJ / cm ² (365 nm reference) in an air atmosphere using an exposure machine (“TME-150RSK” manufactured by Topcon Corporation). And irradiated with light. The coated film after exposure was immersed and developed in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 24 ° C. for 60 seconds, and then washed with water. Thereafter, post-baking was performed in an oven at 230 ° C. for 30 minutes to obtain a colored coating film.
The film thickness of the obtained colored coating film was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The film thickness of the colored coating film obtained by light irradiation under the condition of an exposure amount of 80 mJ / cm ² is A (μm).
Further, a colored coating film was formed in the same manner as above except that the exposure amount at the time of light irradiation was 30 mJ / cm ² (the film thickness of the coating film before the light irradiation was the same as above). The film thickness of the colored coating film obtained by light irradiation under the condition of an exposure amount of 30 mJ / cm ² is defined as B (μm).
The ratio of the thickness B of the colored coating film obtained by irradiation under the conditions of exposure 30 mJ / cm ² with respect to the film thickness A of the colored coating film obtained by irradiation under the conditions of exposure 80 mJ / cm ² (thickness The ratio B / A) was calculated. Table 3 shows the measured values of the film thicknesses A and B and the film thickness ratio B / A.

Claims (4)

A colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D);
The colorant (A) contains a dye,
A colored curable resin composition in which the polymerization initiator (D) includes a polymerization initiator represented by the formula (D-1).

[Wherein, R ^d1 and R ^d2 each independently represent a hydrogen atom, a chain alkyl group which may have a substituent, or a cyclic organic group which may have a substituent, and R ^d1 And R ^d2 together may form a ring,
R ^d3 represents a monovalent organic group,
R ^d4 represents a hydrogen atom, an optionally substituted alkyl group having 1 to 11 carbon atoms, or an optionally substituted aryl group;
dm represents 0 or 1. ]   The colored curable resin composition according to claim 1, wherein the dye contains a dye having a xanthene skeleton.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 3.