JP2013007032A - Colored curable resin composition - Google Patents

Abstract

A colored curable resin composition capable of forming a color filter with high brightness is provided.
A colored curable composition comprising a colorant, a binder resin, a polymerizable compound and a polymerization initiator, wherein the colorant is a colorant comprising a xanthene dye (A1) and a metal complex dye (A2). The metal complex dye (A2) is a complex having an azo dye or methine dye as a ligand and chromium, cobalt or nickel as a central metal, and having an azo dye as a ligand, and is represented by (d-1). Particularly preferred is a metal complex dye having chromium as a central metal.

[Selection figure] None

Description

  The present invention relates to a colored curable resin composition.

  Colored curable resin compositions are used in the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a colored curable resin composition, a colored curable resin composition containing only Orasol Red 3GL (C.I. Solvent Red 130) as a colorant is known (for example, Patent Document 1 (paragraph [ 0085], [0095] etc.)).

JP 2009-163226 A

  Conventionally known colored curable resin compositions as described above may not always be sufficiently satisfactory with respect to the brightness of the obtained color filter.

The present invention provides the following [1] to [7].
[1] A colored curable resin composition comprising a colorant, a binder resin, a polymerizable compound and a polymerization initiator, wherein the colorant is a colorant comprising a xanthene dye (A1) and a metal complex dye (A2).
[2] The metal complex dye (A2) is at least one selected from the group consisting of a compound represented by the formula (3), a compound represented by the formula (4), and a compound represented by the formula (6). [1] The colored curable resin composition according to [1].

[In the formula (3), R ^{31 to} R ⁴⁸ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁵¹ , —SO ₃ H or — Represents SO ₂ CH ₃ .
R ⁴⁹ and R ⁵⁰ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁵¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ^{1 to} A ⁴ each independently represent * —O—, * —O—CO—, or * —CO—O—. * Represents a bond with M.
M represents Cr or Co.
n represents an integer of 1 to 5.
D ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

[In the formula (4), R ^{52 to} R ⁶⁰ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁶² , —SO ₃ H or It represents a -SO ₂ CH _3.
R ⁶¹ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁶² each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ⁵ and A ⁶ each independently represent * —O—, * —O—CO— or * —CO—O—.
* Represents a bond with M1.
M1 represents Cr or Co.
n1 represents the integer of 0-2.
D1 ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

Wherein (6), R ⁸¹ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, hydrogen atoms contained in the saturated hydrocarbon ^{group, -OH, -OR 88, -CO-} OR ⁸⁸ , —O—COR ⁸⁸ , —CONR ⁸⁸ R ⁸⁹ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and —CH ₂ contained in the saturated hydrocarbon group -May be replaced by at least one of -O- and -CO-.
R ⁸² represents a hydrogen atom, -CN, or -CONH _2.
R ⁸³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ⁸⁴ to R ^87, independently of one ^{another, -R 88, -OR 88, -CO} -OR 88, -COR 88, -OCO-OR 88, -O-COR 88, -CN, -NO 2, a halogen atom represents _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 88 R 89 or -NR ⁹¹ R ^92. R ⁸⁴ and R ⁸⁵ , R ⁸⁵ and R ⁸⁶ , and R ⁸⁶ and R ⁸⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with —OR ⁹⁰ .
R ⁹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ⁹¹ and R ⁹² may combine with each other to form a ring containing a nitrogen atom.
A ^{11 to} A ¹⁴ each independently represent * —O—, * —O—CO— or * —CO—O—. * Represents a bond with M ² .
M ² represents Cr or Co.
n2 represents an integer of 1 to 5.
D2 ⁺ represents a monovalent cation derived from a compound having a hydrone, a monovalent metal cation or a xanthene skeleton. ]

[3] The colored curable resin according to [1] or [2], wherein the metal complex dye (A2) is a dye containing a metal complex dye (A2-1) having a maximum absorption wavelength in a range of 490 nm to 580 nm. Composition.
[4] The ratio (A1: A2) of the content of the xanthene dye (A1) to the content of the metal complex dye (A2) is 1:99 to 99: 1 on a mass basis [1] to [1] 3] The colored curable resin composition according to any one of [3].
[5] The colored curable resin composition according to any one of [1] to [4], wherein the polymerization initiator is a polymerization initiator containing an oxime compound.
[6] A color filter formed from the colored curable resin composition according to any one of [1] to [5].
[7] A display device including the color filter according to [6].

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

The colored curable resin composition of the present invention contains a colorant (A), a binder resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the colorant (A) is a xanthene dye ( A colorant containing A1) and a metal complex dye (A2).
By using the colorant (A) containing the xanthene dye (A1) and the metal complex dye (A2), the brightness is improved.

  The ratio (A1: A2) of the content of the xanthene dye (A1) and the content of the metal complex dye (A2) in the colorant (A) is 1:99 to 99: 1 on a mass basis. Preferably, 1:99 to 75:25 is more preferable, and 2:98 to 60:40 is more preferable. When the ratio (A1: A2) is within the above range, a color filter with higher brightness can be obtained.

The xanthene dye (A1) is a dye containing a compound having a xanthene skeleton in the molecule.
Examples of the xanthene dye include C.I. I. Acid Red 51, 52 (Formula (A1-2)), 87, 92, 94 (Rose Bengal), 289 (Formula (A1-3)), 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G) (Formula (A1-4)), 8, C.I. I. Basic Violet 10 (Rhodamine B), C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like.

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

[In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. .
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ are the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, and the saturated aliphatic carbon group —CH ₂ — contained in the hydrogen group may be replaced by —O—, —CO—, —NH— or —NR ¹² —.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and R ⁹ and R ¹⁰ are bonded to each other. A 3- to 10-membered heterocyclic ring containing a nitrogen atom may be formed. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, —CO—, — NH— or —NR ¹² — may be substituted.
R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.
R ¹² represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by 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. It is done.

In the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ , the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, —R ⁸ , —OH, —OR. ⁸ , —SO ₃ ⁻ , —SO ₃ H, —SO ₃ ^— Z ⁺ , —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ^8, or —SO ₂ NR ⁹ R ¹⁰ may be substituted. . Among these _{^{substituents, -SO 3 -, -SO 3 H}} , -SO 3 - is preferably at least one selected from Z ⁺ and the group consisting of _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and More preferred is at least one selected from the group consisting of —SO ₂ NR ⁹ R ¹⁰ . In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, the color curable resin composition containing the compound (1) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{8 to} R ¹² include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Linear alkyl groups such as n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, n-icosyl group; isopropyl group, isobutyl group, isopentyl Branched chain alkyl groups such as a group, neopentyl group and 2-ethylhexyl group; an alicyclic 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 Formula saturated hydrocarbon groups are mentioned.

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

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

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When the compound (1) has ⁺ N (R ¹¹ ) ₄ , when R ¹¹ is these groups, a color filter with few foreign matters can be formed from the colored curable resin composition containing the compound (1).

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

  As said xanthene dye (A1), the dye containing the compound (henceforth a "compound (2)") represented by Formula (2) is more preferable. When the compound (2) is used, the content of the compound (2) in the xanthene dye (A1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (2) as the xanthene dye (A1).

[In 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 which may have a substituent. .
R ²⁵ is, -SO ₃ ^- represents a Z1 ⁺ or _{^{-SO 2 NHR 26 -, -SO 3}} H, -SO 3.
m1 represents the integer of 0-5. When m1 is an integer of 2 or more, the plurality of R ²⁵ are the same or different.
a1 represents an integer of 0 or 1.
X1 represents a halogen atom.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z1 ⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ .
R ²⁷ each independently represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group. ]

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{21 to} R ²⁴ include the same groups as those exemplified as the aromatic hydrocarbon group in R ^{1 to} R ⁴ . Hydrogen atoms contained in the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, may be substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26.
As a combination of R ^{21 to} R ²⁴ , R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z1 +, those substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ²⁶ preferred. A more preferred combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group atom, -SO ₃ ^- are those which are substituted with Z1 ⁺ or -SO ₂ NHR ^26. When R ^{21 to} R ²⁴ are these groups, a color filter having excellent heat resistance can be formed from the colored curable resin composition containing the compound (2).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by 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 each independently represent a hydrogen atom, a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When the compound (2) has —SO ₃ R ²⁶ and / or —SO ₂ NHR ²⁶ , when R ²⁶ is any of these groups, the colored curable resin composition containing the compound (2) has no occurrence of foreign matters. Fewer color filters can be formed.

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

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

Examples of the compound (2) include compounds represented by the formulas (1-1) to (1-23). In the formula, R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group. Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. A quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), and formula (1-12).

  The xanthene dye (A1) preferably has a maximum absorption wavelength in the range of 490 nm to 580 nm, more preferably in the range of 510 nm to 560 nm, and still more preferably in the range of 520 nm to 540 nm. The maximum absorption wavelength can be obtained from an absorption spectrum obtained by measuring a solution obtained by dissolving a dye in a solvent using a spectrophotometer, and will be described in detail later.

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

  The metal complex dye (A2) is a dye obtained by complexing a metal atom with a dye molecule containing a group capable of complexing with a metal atom in the molecule.

  Examples of the metal complex dye (A2) include C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161; C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99; C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Acid red 211, and metal complex dyes described in JP 2010-170117 A. These metal complex dyes (A2) may be used alone or in combination of two or more.

Examples of the dye molecule (ligand) include azo dyes and methine dyes, with azo dyes being preferred.
Examples of the metal atom include chromium, cobalt, nickel and the like, and chromium and cobalt are preferable.
The metal complex dye (A2) includes a 1: 1 type metal complex dye having a bond ratio of metal atoms to dye molecules of 1: 1, and a 1: 2 type metal complex dye having a ratio of 1: 2. And a 1: 2 metal complex dye is preferred.

  The metal complex dye (A2) is preferably a compound represented by formula (3), formula (4) or formula (6).

[In the formula (3), R ^{31 to} R ⁴⁸ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁵¹ , —SO ₃ H or — Represents SO ₂ CH ₃ .
R ⁴⁹ and R ⁵⁰ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁵¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ^{1 to} A ⁴ each independently represent * —O—, * —O—CO—, or * —CO—O—. * Represents a bond with M.
M represents Cr or Co.
n represents an integer of 1 to 5, and may be an integer of 2 to 5.
D ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

[In the formula (4), R ^{52 to} R ⁶⁰ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁶² , —SO ₃ H or It represents a -SO ₂ CH _3.
R ⁶¹ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁶² each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ⁵ and A ⁶ each independently represent * —O—, * —O—CO— or * —CO—O—.
* Represents a bond with M1.
M1 represents Cr or Co.
n1 represents the integer of 0-2.
D1 ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ^{31 to} R ⁴⁸ , R ⁵¹ , R ^{52 to} R ⁶⁰ , and R ⁶² include a methyl group, ethyl group, n-propyl group, n- Linear alkyl groups such as butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group; isopropyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1, Branched chain such as 1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 1,1,5,5-tetramethylhexyl group An alkyl group is mentioned.
Of R ^{31 to} R ⁴⁸ , at least one is preferably a nitro group. Further, among R ⁵² to R ^60, it is preferred that at least one is a nitro group. By having a nitro group, the spectral concentration of the compound tends to increase.
R ⁴⁹ and R ⁵⁰ are preferably methyl groups.

Examples of the alkoxyalkyl group having 2 to 15 carbon atoms represented by R ⁵¹ and R ⁶² include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a 1-ethoxypropyl group, and 2-ethoxy. Propyl group, 1-ethoxy-1-methylethyl group, 2-ethoxy-1-methylethyl group, 1-isopropoxypropyl group, 2-isopropoxypropyl group, 1-isopropoxy-1-methylethyl group, 2- Examples include isopropoxy-1-methylethyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

In the above formulas (3) and (4), preferred combinations of groups other than D and D1 are as follows.
That is, in equation (3),
One of R ^{31 to} R ³⁹ is a hydrogen atom or a nitro group, one is one selected from a hydrogen atom, SO ₂ NHR ⁵¹ , —SO ₃ H, and —SO ₂ CH ₃ , and the rest is a hydrogen atom And
One of R ^{40 to} R ⁴⁸ is a hydrogen atom or a nitro group, one is one selected from a hydrogen atom, SO ₂ NHR ⁵¹ , —SO ₃ H, and —SO ₂ CH ₃ , and the rest is a hydrogen atom And
R ⁴⁹ and R ⁵⁰ are methyl groups,
R ⁵¹ is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms,
Two of A ^{1 to} A ⁴ are * —O—, and the rest are the same * —O— or * —O—CO—,
M is Cr,
A combination in which n is 1 is preferable.
In equation (4):
One of R ^{52 to} R ⁶⁰ is a nitro group, one is one selected from SO ₂ NHR ⁶² , —SO ₃ H, and SO ₂ CH ₃ , and the remainder is a hydrogen atom,
R ⁶¹ is a methyl group,
R ⁶² is a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 8 carbon atoms,
One of A ^{5 to} A ⁶ is * -O-, the rest is * -O- or * -O-CO-,
M1 is Cr or Co;
n1 is preferably a combination of 0 or 1.

[In Formula (6),
R ⁸¹ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is —OH, —OR ⁸⁸ , —CO—OR ⁸⁸ , —O—COR ^88. , -CONR ⁸⁸ R ⁸⁹ , a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group may be —O— or It may be replaced by -CO-.
R ⁸² represents a hydrogen atom, -CN, or -CONH _2.
R ⁸³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ⁸⁴ to R ^87, independently of one ^{another, -R 88, -OR 88, -CO} -OR 88, -COR 88, -OCO-OR 88, -O-COR 88, -CN, -NO 2, a halogen atom represents _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 88 R 89 or -NR ⁹¹ R ^92. R ⁸⁴ and R ⁸⁵ , R ⁸⁵ and R ⁸⁶ , and R ⁸⁶ and R ⁸⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with —OR ⁹⁰ .
R ⁹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ⁹¹ and R ⁹² may combine with each other to form a ring containing a nitrogen atom.
A ^{11 to} A ¹⁴ each independently represent * —O—, * —O—CO— or * —CO—O—. * Represents a bond with M ² .
M ² represents Cr or Co.
n2 represents an integer of 1 to 5.
D2 ⁺ represents a monovalent cation derived from a compound having a hydrone, a monovalent metal cation or a xanthene skeleton. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 12 carbon atoms represented by R ⁸¹ include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n- Linear saturated hydrocarbon groups such as heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group;
Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, methylpentyl group, ethylbutyl group, methylhexyl group, ethylpentyl group, propylbutyl group, (methylethyl) butyl group, (methylethyl) ( Methyl) propyl, methylheptyl, ethylhexyl, propylpentyl, (methylethyl) pentyl, butylbutyl, (butyl) (methyl) butyl, (dimethylethyl) (butyl) butyl, dimethylpropyl, dimethyl Butyl, (ethyl) (methyl) propyl, dimethylpentyl, (ethyl) (methyl) butyl, dimethylhexyl, (ethyl) (methyl) pentyl, (propyl) (methyl) butyl, (methylethyl) ) (Methyl) butyl group, diethyl butyl group, etc. Chain saturated hydrocarbon group;
Examples thereof include alicyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecyl group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁸³ include a linear saturated hydrocarbon group having 4 or less carbon atoms and a branched chain having 4 or less carbon atoms among the groups exemplified for R ^81. A saturated saturated hydrocarbon group can be exemplified.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ⁸⁸ , R ⁸⁹ , R ⁹¹ and R ⁹² include those having 8 or less carbon atoms among the above groups exemplified as R ^81. It can be illustrated. Furthermore, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a 2-methylpropenyl group, and the like are also included.

Examples of the aralkyl group having 7 to 12 carbon atoms in R ⁸⁸ and R ⁸⁹ include a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, and a naphthylethyl group.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ⁸⁸ , R ⁸⁹ and R ⁹⁰ include a phenyl group, a toluyl group, a xylyl group and a naphthyl group.
Examples of the monovalent saturated hydrocarbon group having 1 to 8 carbon atoms represented by R ⁹⁰ include those having 8 or less carbon atoms among the groups exemplified for R ⁸¹ .

Examples of the acyl group having 2 to 8 carbon atoms in R ⁹¹ and R ⁹² include formyl group, acetyl group, propionyl group, butanoyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group and the like.

In R ⁸¹ , the saturated hydrocarbon group in which —CH ₂ — is replaced by —O— or —CO— is, for example, saturated containing an oxo group such as an acetyl group, an oxobutyl group, an oxopentyl group, and an oxohexyl group. A hydrocarbon group;
Fragrance such as phenacyl group, oxo (naphthyl) ethyl group, oxo (hydroxyphenyl) ethyl group, oxo (hydroxynaphthyl) ethyl group, oxo (methoxyphenyl) ethyl group, oxo (phenyl) propyl group, oxo (naphthyl) propyl group An oxo group-containing saturated hydrocarbon group substituted with an aromatic group; a saturated hydrocarbon group in which one —CH ₂ — is replaced with —CO—; and a 2- [2- (acetyloxy) acetoxy] ethyl group, Groups formed by alkyl groups such as 2- (2-ethylhexanoyloxy) ethyl group, 2- [2- (methoxycarbonyl) ethylcarbonyloxy] ethyl group, alkylene groups, and ester bonds;
2-benzoyl alkylene group such as methacryloyloxyethyl group, an aromatic ring, and a group formed by an ester bond; one -CH ₂ such - is replaced by -CO-, one -CH ₂ - is -O A saturated hydrocarbon group replaced by-.

In the above formula (6), preferred combinations of groups other than D2 are:
R ⁸¹ is an alkyl group having 1 to 4 carbon atoms; a hydroxyalkyl group having 1 to 4 carbon atoms; a group formed by an alkyl group, an alkylene group, and two ester bonds, an alkylene group, an aromatic ring, and one ester Any of the groups formed with the bond,
R ⁸² is -CN,
R ⁸³ is an alkyl group having 1 to 4 carbon atoms,
Three of the R ⁸⁴ to R ⁸⁷ is an R ⁸⁸ is a hydrogen atom, an R ⁸⁸ or -NR ⁹¹ R ⁹² one of which is a hydrogen atom remains, R ⁹¹ and R ⁹² constituting the -NR ⁹¹ R ⁹² One of them is a hydrogen atom, the other is an acyl group having 2 to 4 carbon atoms,
Two of A ^{11 to} A ¹⁴ are * —O—, and the rest are the same * —O— or * —O—CO—;
M ² is Cr,
n2 is a combination that becomes 1.

Examples of monovalent metal cations represented by D ⁺ , D1 ⁺ , and D2 ⁺ include lithium cations, sodium cations, and potassium cations. Examples of the monovalent cation derived from the compound having a xanthene skeleton represented by D ⁺ , D1 ⁺ , and D2 ⁺ include a cation represented by the formula (5). Since the brightness of the color filter formed from the colored curable resin composition can be improved, the D ⁺ , D 1 ⁺ , and D 2 ⁺ are preferably monovalent cations derived from a compound having a xanthene skeleton.

[In Formula (5), each of R ^{63 to} R ⁶⁶ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. To express.
R ⁶⁷ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 6 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, or — (R ⁷⁰ —O) _w —R ⁷¹ .
^R70 represents an ethylene group, a propane-1,3-diyl group, or a propane-1,2-diyl group.
R ⁷¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
w represents an integer of 1 to 4; ]

Examples of the monovalent saturated hydrocarbon group having 1 to 6 carbon atoms represented by R ^{63 to} R ⁶⁷ include those having 1 to 6 carbon atoms among those exemplified as the saturated hydrocarbon group in R ^{31 to} R ^48. Can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{63 to} R ⁶⁷ include phenyl group, toluyl group, xylyl group, mesityl group, propylphenyl group, and butylphenyl group. It is done.
R ^{63 to} R ⁶⁶ are each independently preferably a hydrogen atom or an ethyl group.
R ⁶⁷ is preferably a hydrogen atom, an ethyl group, or — (R ⁷⁰ —O) _w —R ⁷¹ .

- The _{^{(R 70 -O) w -R 71}} , 2- (2- hydroxyethoxy) ethyl and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group are preferable, and 2- [2- (2 -Hydroxyethoxy) ethoxy] ethyl group is more preferred.

  Examples of the metal complex dye (A2) represented by the formula (3) include C.I. I. Solvent Red 130 (compound represented by Formula (3-1)), C.I. I. Solvent Red 125 (compound represented by Formula (3-2)), C.I. I. Solvent Yellow 21 (compound represented by formula (3-3)), compound represented by formula (3-4), compound represented by formula (3-5), and JP 2010-170116 A or Examples include compounds described in JP2011-215572A.

  Examples of the metal complex dye (A2) represented by the formula (4) include C.I. I. Solvent Orange 56 (compound represented by Formula (4-1)) and the like.

  Examples of the metal complex dye (A2) represented by the formula (6) include Japanese Patent Application Laid-Open Nos. 2011-148990, 2011-148993, 2011-148994, and 2011-14895. And the compounds described. Particularly preferred metal complex dyes of the formula (6) include anionic structures represented by the formulas (6-1) to (6-6), and most preferred metal complex dyes of the formula (6) are represented by the formulas (6-7). ).

  Among these, as the metal complex dye (A2), a metal complex dye (A2-0) having a maximum absorption wavelength in the range of 410 nm to 580 nm is preferable, and a metal complex salt having a maximum absorption wavelength in the range of 490 nm to 580 nm. A dye (A2-1) is more preferable. The maximum absorption wavelength of the metal complex dye (A2-1) is preferably 570 nm or less, and more preferably 560 nm or less. By including a dye having such a maximum absorption wavelength, there is a tendency to effectively absorb light in a transmission region (so-called floating in the transmission spectrum) existing below the maximum absorption wavelength of the xanthene dye (A1). A color filter with high brightness and contrast can be obtained.

  The absolute value of the difference between the maximum absorption wavelength of the metal complex dye (A2-1) and the maximum absorption wavelength of the xanthene dye (A1) is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more. It is preferably 100 nm or less, more preferably 80 nm or less, still more preferably 50 nm or less. When 2 or more types of metal complex dye (A2-1) and / or xanthene dye (A1) are included, it is preferable that all satisfy | fill the said relationship. When the absolute value of the difference between the maximum absorption wavelengths of the metal complex dye (A2-1) and the xanthene dye (A1) is within the above range, a color filter having higher brightness and contrast can be obtained.

  When the metal complex dye (A2-1) is used, the metal complex dye (A2-1-1) having a maximum absorption wavelength in the range of 490 nm to 535 nm and the maximum absorption wavelength in the range of more than 535 nm to 580 nm or less. It is preferable to use together with the metal complex dye (A2-1-2). By including a dye having such a maximum absorption wavelength, a color filter with higher brightness can be obtained.

  In this case, the content of the metal complex dye (A2-1-2) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass in the metal complex salt dye (A2-1). % Or more, preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. When the content of the metal complex dye (A2-1-2) is within the above range, a color filter having higher brightness and contrast can be obtained.

  When the metal complex dye (A2-2) having a maximum absorption wavelength in the range of 410 nm or more and less than 490 nm is used as the metal complex dye (A2-0), it should be used in combination with the metal complex dye (A2-1). Is preferred. The maximum absorption wavelength of the metal complex dye (A2-2) is preferably 430 nm or more, more preferably 470 nm or less, and more preferably 450 nm or less. By using the metal complex dye (A2-1) and the metal complex dye (A2-2) in combination, the light in the transmission region existing below the maximum absorption wavelength of the xanthene dye (A1) is more effectively absorbed. Therefore, the brightness and contrast of the obtained color filter are further increased.

  The absolute value of the difference between the maximum absorption wavelength of the metal complex dye (A2-2) and the maximum absorption wavelength of the xanthene dye (A1) is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more. It is preferably 120 nm or less, more preferably 100 nm or less, still more preferably 90 nm or less. When 2 or more types of metal complex salt dye (A2-2) and / or xanthene dye (A1) are included, it is preferable that all satisfy | fill the said relationship. If the absolute value of the difference between the maximum absorption wavelengths of the metal complex dye (A2-2) and the xanthene dye (A1) is within the above range, a color filter with higher brightness can be obtained.

  The absolute value of the difference between the maximum absorption wavelength of the metal complex dye (A2-1) and the maximum absorption wavelength of the metal complex dye (A2-2) is preferably 5 nm or more, more preferably 10 nm or more, still more preferably It is 30 nm or more, 150 nm or less is preferable, More preferably, it is 120 nm or less, More preferably, it is 100 nm or less. When 2 or more types of metal complex salt dye (A2-1) and / or metal complex dye (A2-2) are included, it is preferable that all satisfy | fill the said relationship. When the absolute value of the difference between the maximum absorption wavelengths of the metal complex dye (A2-1) and the metal complex dye (A2-2) is within the above range, a color filter having higher brightness and contrast can be obtained.

In this case, the content of the metal complex dye (A2-1) is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more with respect to the metal complex salt dye (A2). 100 mass% or less is preferable. When the content of the metal complex dye (A2) is within the above range, a color filter with high brightness and high contrast can be obtained.
As the metal complex dye (A2), a commercially available metal complex dye (for example, “ORASOL Red G”, “ORASOL Red 3GL”, “Neozapon Yellow 157” manufactured by BASF) can be used. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-170117.

The colorant (A) may further contain a pigment (A3) together with a xanthene dye (A1) and a metal complex dye (A2).
Examples of the pigment (A3) include compounds classified as pigments according to a color index (published by The Society of Dyers and Colorists), such as C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as CI Pigment Green 7, 36, 58; I. C.I. brown pigments such as CI Pigment Brown 23 and 25; I. And black pigments such as CI Pigment Black 1 and 7.

  Among these, the pigment (A3) includes C.I. I. Pigment yellow 138, 139, 150; I. Pigment red 177, 209, 242 and 254; C.I. I. Pigment Violet 23 is preferable. By including these pigments, it is easy to optimize the transmission spectrum and the chemical resistance is improved. These pigments may be used alone or in combination of two or more.

  The pigment (A3) preferably has a uniform particle size. In addition, the pigment (A3) is optionally treated by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, etc., sulfuric acid fine particles A pulverization process using a chemical method or the like, a cleaning process using an organic solvent or water to remove impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed.

When the pigment (A3) is used, it is preferably used in the form of a pigment dispersion. In this case, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by adding the pigment dispersant to the solution and performing the pigment dispersion treatment.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) (BASF) ), Ajisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie), and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment (A3). When the amount of the pigment dispersant used is in the above range, a more uniformly dispersed pigment dispersion can be obtained.

  When the pigment (A3) is included, the content ratio in the colorant (A) is preferably 1% by mass to 90% by mass, and more preferably 3% by mass to 80% by mass. By setting such a ratio, the transmission spectrum can be easily optimized, and the resulting color filter tends to be excellent in contrast, brightness, heat resistance, and chemical resistance.

  The content of the colorant (A) is preferably 5% by mass to 60% by mass, more preferably 8% by mass to 55% by mass with respect to the solid content in the colored curable resin composition. Preferably it is 10 mass%-50 mass%. Here, solid content means the sum total of the component except the solvent in colored curable resin composition. When the content of the colorant (A) is in the above range, a desired spectral and color density can be obtained when a color filter is used, and a necessary amount of binder resin or polymerizable compound is contained in the composition. Therefore, a color filter having sufficient mechanical strength can be formed.

The colored curable resin composition of the present invention contains a binder resin (B). The binder resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the binder resin (B) include the following resins [K1] to [K6].
[K1] at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (a) (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”).
[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) Copolymer).
[K3] A copolymer of (a) and (c).
[K4] A resin obtained by reacting (b) with a copolymer of (a) and (c).
[K5] A resin obtained by reacting (a) with a copolymer of (b) and (c).
[K6] A resin obtained by reacting a copolymer of (b) and (c) with (a) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid , Mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4- Unsaturated dicarboxylic acids such as 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 [ 2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2 Bicyclounsaturated compounds containing a carboxy group such as ene; 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, etc. Unsaturated dicarboxylic acid anhydrides; succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], etc. Unsaturated monocarboxylic acid [(meth) acryloyloxy alkyl] esters; alpha-(hydroxymethyl) such as acrylic acid, unsaturated acrylates, and the like containing a hydroxy group and a carboxy group in the same molecule. These (a) may be used independently and may use 2 or more types together.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility of the resin in an alkaline aqueous solution.

The (b) is, for example, a polymerizable compound 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) and an ethylenically unsaturated bond. It is. As said (b), the monomer which has C2-C4 cyclic ether and (meth) acryloyloxy group is preferable.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

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

  Examples of (b1) include a monomer (b1-1) having a structure in which an aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-1)”), an alicyclic group And a monomer (b1-2) having a structure in which a saturated hydrocarbon is epoxidized (hereinafter may be referred to as “(b1-2)”).

  Examples of (b1-1) include 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) The Tylene, 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 (registered trademark) 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl. (Meth) acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100; Daicel Chemical Industry ( Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

[In Formula (I) and Formula (II), R ^b1 and R ^b2 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.
L ¹ and L ² each independently represent a single bond, —R ^b3 —, * —R ^b3 —O—, * —R ^b3 —S—, * —R ^b3 —NH—. R ^b3 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 represented by R ^b1 or R ^b2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. .
Examples of the alkyl group having 1 to 4 carbon atoms and having a hydrogen atom substituted with hydroxy include, for example, a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, and a 2-hydroxypropyl group. 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group Etc.
R ^b1 and R ^b2 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 represented by R ^b3 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.
L ¹ and L 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 and a * —CH ₂ CH ₂ —O— group are mentioned.

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15) Is mentioned. More preferably, Formula (I-1), Formula (I-7), Formula (I-9), and Formula (I-15) are mentioned.

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

  The compound represented by the formula (I) and the compound represented by the formula (II) can be used alone. Moreover, they can be used together in arbitrary ratios. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio is a molar ratio, preferably 5:95 to 95 in the formula (I): the formula (II). : 5, more preferably 10:90 to 90:10, still more preferably 20:80 to 80:20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane, and 3-ethyl-3-acryloyloxymethyl. Examples thereof include oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane.

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

  (B) is a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. Preferably there is. Furthermore, the monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferable in that the storage stability of the colored curable resin composition is excellent.

  Examples of (c) (a polymerizable monomer different from the above (a) and (b)) include, for example, (meth) acrylic acid esters, dicarboxylic acid diesters, bicyclounsaturated compounds, and dicarbonylimide derivatives. , Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3- Examples thereof include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5. 2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. In addition, “tricyclodecyl (meth) Acrylate " Sometimes referred.), Tricyclo (Meta) acrylate (the art, "dicyclopentenyl (meth acrylate as trivial name)" [5.2.1.0 ^{2, 6]} decene-8-yl is said to Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate And (meth) acrylic acid esters such as benzyl (meth) acrylate; hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

  Examples of the dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

  Examples of the bicyclo unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, and 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-methyl Bicyclo [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-phenoxycarbonyl Bicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbo) Le) bicyclo [2.2.1] hept-2-ene, and the like.

  Examples of the dicarbonylimide derivatives include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, and N-succinimidyl-6. -Maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

  Said (c) may be used independently and may use 2 or more types together. Among these, as the component (c), from the viewpoint of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept- 2-ene and the like are preferable.

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].
Structural unit derived from (a); 2 to 50 mol% (more preferably 10 to 45 mol%)
Structural unit derived from (b); 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.

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

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction vessel, and stirred, heated, and kept warm in a deoxygenated atmosphere. 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. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer, and a solvent described later can be used as the solvent (E) of the colored curable resin composition.

  In addition, when using the obtained copolymer for preparation of a colored curable resin composition, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or reprecipitation. You may use what was taken out as solid (powder) by methods, such as. In particular, since the solvent contained in the colored curable resin composition of the present invention is used as a solvent during the polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition. The production process of the colored curable resin composition 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].
Structural unit derived from (a); 4-45 mol% (more preferably 10-30 mol%)
Structural unit derived from (b); 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 of the colored curable resin composition, the developability during pattern production, the solvent resistance of the resulting color filter, the heat resistance and the mechanical strength. Tend to be better.

Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].
Specifically, a predetermined amount of (a), (b) 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. 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].
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, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of [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).
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, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( (Dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (for example, hydroquinone and the like) are placed in a flask and reacted at, for example, 60 to 130 ° C. for 1 to 10 hours to obtain a resin [K4]. .
The amount of (b) used 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 is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 mass% with respect to the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5% by 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) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following ranges with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol% (more preferably 10-90 mol%)
Structural unit derived from (c); 5-95 mol% (more preferably 10-90 mol%)

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

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

As the binder resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) Resin [K2] such as acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate Resin [K3] such as silicate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; glycidyl (meth) acrylate in benzyl (meth) acrylate / (meth) acrylic acid copolymer Added resin, resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / ( Resin [K4] such as a resin in which glycidyl (meth) acrylate is added to a (meth) acrylic acid copolymer; (meth) acrylic acid is reacted with a tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with a copolymer of [K5]; a resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate In addition, resin [K6] such as a resin obtained by further reacting with tetrahydrophthalic anhydride.
These resins may be used alone or in combination of two or more.

Among these, as the binder resin (B), the resin [K1] and the resin [K2] are preferable, and include a structural unit derived from 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate. The resin [K2] containing a structural unit derived from the resin [K1] and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate is more preferable.

The polystyrene-reduced weight average molecular weight of the binder resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. It is. When the average molecular weight is within the above range, the solubility of the unexposed area in the developer tends to be high, and the remaining 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 binder resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.
The acid value of the binder resin (B) is preferably 50 to 180 mg-KOH / g, more preferably 60 to 150 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  The content of the binder resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 65% by mass with respect to the solid content of the colored curable resin composition. 55% by mass. When the content of the binder resin (B) is in the above range, when forming a pattern, the solubility of the unexposed portion in the developer tends to be high.

  The colored curable resin composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. Preferably, a (meth) acrylic acid ester compound is used.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octane. (Meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified penta Erythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Le-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate. Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable. These polymerizable compounds may be used alone or in combination of two or more.
The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  Content of polymeric compound (C) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a colored curable resin composition, More preferably, it is 13-60 mass%, More preferably, 17- 55% by mass. When the content of the polymerizable compound (C) is within the above range, curing is sufficiently performed by exposure in pattern formation, the remaining film ratio of the exposed portion in development is improved, and an undercut enters the pattern. This is preferable because it tends to be difficult and the adhesiveness tends to be good.

The colored curable resin composition of the present invention contains a polymerization initiator (D). The polymerization initiator (D) is not particularly limited as long as it generates an active radical by the action of light or heat and can initiate polymerization of the polymerizable compound (C), and a known radical polymerization initiator can be used. Can be used.
The polymerization initiator (D) is preferably a compound that generates an active radical by the action of light, more preferably an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an oxime compound, and a biimidazole compound, and a polymerization start containing an oxime compound. More preferred are agents.

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

Examples of the alkylphenone compound include an α-aminoalkylphenone compound having a partial structure represented by the formula (d2), an α-alkoxyalkylphenone compound having a partial structure represented by the formula (d3), and an α-hydroxyalkyl. And phenone compounds.
Examples of the α-aminoalkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane. -1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2- (4-methylphenylmethyl) butan-1-one, and the like. Examples of commercially available products include Irgacure (registered trademark) 369, 379, and 907 (above, manufactured by BASF).
Examples of the α-alkoxyalkylphenone compound include diethoxyacetophenone and benzyldimethyl ketal.
Examples of the α-hydroxyalkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1 -One, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl). ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2- Methylphenyl) ete Le] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

  Examples of the oxime compound include an O-acyl oxime compound, and the O-acyl oxime compound is a compound having a partial structure represented by the formula (d1).

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethi -6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H -Carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine preferable. When these oxime compounds are used, a high brightness color filter tends to be obtained.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Nyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913). Preferably, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5 Examples include 5'-tetraphenylbiimidazole and 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole.

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

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 5 to 100 parts by mass of the total amount of the binder resin (B) and the polymerizable compound (C). 25 parts by mass. When the content of the polymerization initiator (D) is in the above range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

The colored curable resin composition of the present invention may further contain a polymerization initiation assistant (D1). When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D). The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation assistant (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like, and thioxanthone compounds are preferred.

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

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

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

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

These polymerization initiation assistants may be used alone or in combination of two or more.
Moreover, when using a polymerization start adjuvant (D1), the usage-amount is preferably 0.1-30 mass parts with respect to 100 mass parts of total amounts of binder resin (B) and polymeric compound (C), More preferably, it is 1-20 mass parts. Moreover, Preferably it is 20-100 mass parts with respect to 100 mass parts of content of a polymerization initiator (D), More preferably, it is 30-80 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a pattern can be formed with high sensitivity, and a color filter with higher brightness tends to be obtained.

The colored curable resin composition of the present invention preferably contains a solvent (E).
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- Solvents not containing CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be used.

  Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Examples include butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

  Examples of the ether solvent 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, di Chi glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, 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 ester 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 the like.

  Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, Examples include isophorone.

  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, mesitylene and the like.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C. or more and 180 ° C. or less at 1 atm (101.325 kPa) is preferable from the viewpoints of coating properties and drying properties. Among them, 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, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, More preferred are 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and the like.

  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 with respect to the colored curable resin composition. 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 when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

The colored curable resin composition of the present invention may further contain a surfactant (F).
Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

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

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, R183, 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.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.

  The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.1% by mass with respect to the colored curable resin composition. Below, more preferably 0.01 mass% or more and 0.05 mass% or less. However, the content of the pigment dispersant is not included in the content of the surfactant (F). When the content of the surfactant (F) is in the above range, the flatness of the coating film can be improved.

  The colored curable resin composition of the present invention includes various additives such as fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, and the like as necessary. May be included.

The colored curable resin composition of the present invention includes, for example, a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. , Surfactant (F), polymerization initiation assistant (D1), and other components can be mixed.
When the pigment (A3) is included, the pigment (A3) is previously mixed with a part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. It is preferable. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and binder resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The xanthene dye (A1) and the metal complex dye (A2) may be previously dissolved in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

Examples of a method for forming a color filter pattern using the colored curable resin composition of the present invention include a photolithographic method and an inkjet method. In order to form a pattern by the photolithographic method, it is applied onto a substrate or another resin layer (for example, another colored curable resin composition layer previously formed on the substrate), and a volatile component such as a solvent. Is removed (dried) to form a colored layer, and the colored layer is exposed through a photomask and developed. In the photolithography method described above, a coating film having no pattern can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the pattern or coating film to be produced is not particularly limited, and can be appropriately adjusted depending on the material used, application, etc. For example, 0.1-30 μm, preferably 1-20 μm, more preferably 1-6 μm. is there.

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 substrate Aluminum, silver, silver / copper / palladium alloy thin film, etc. are used. On these substrates, another color filter layer, resin layer, transistor, circuit, or the like may be formed.
Examples of the coating method include spin coating, slit coating, and slit-and-spin coating.

  As a method of forming each color pixel by the photolithography method, a known or commonly used method can be used. For example, it can be produced as follows.

The colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by drying by heating (pre-baking) and / or drying under reduced pressure to obtain a smooth coating film.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coating film after drying is not particularly limited and can be appropriately adjusted depending on the material used, application, etc., and is, for example, 0.1 to 20 μm, preferably 0.5 to 6 μm.

After drying, the coating film is exposed through a photomask for forming a target pattern. The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended application 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. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an apparatus such as a mask aligner or a stepper because the entire exposed surface can be irradiated with parallel rays uniformly and accurate alignment between the mask and the substrate can be performed.

After exposure, a pattern can be obtained by contacting with the developer and dissolving and removing a predetermined portion, for example, an unexposed portion, in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide and the like is preferable. 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, you may post-bake as needed. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  According to the colored curable resin composition of the present invention, it is possible to produce a red color filter particularly excellent in lightness. The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state image sensor, and the like.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
A mixture of a compound represented by formula (A1-1a) and a compound represented by formula (A1-1b) (manufactured by Chugai Kasei Co., Ltd., trade name Chugai Aminol Fast Pink R) is added to a flask equipped with a condenser and a stirrer. 15 parts, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and represented by xanthene dye A1-1 (formula (A1-1-1) to formula (A1-1-8). 11.3 parts of a mixture of the following compounds).

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 15 parts of a dye represented by the formula (A1-2a) (manufactured by Chugai Kasei Co., Ltd.), 150 parts of chloroform and 7.1 parts of N, N-dimethylformamide. While maintaining the temperature at 20 ° C. or lower, 8.7 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 10 parts of 2-ethylhexylamine and 17.7 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and represented by xanthene dye A1-2 (formula (A1-2-1) to formula (A1-2-7). 12.7 parts).

Synthesis example 3
After adding 80 parts of water to 10.5 parts of 2-amino-4-nitrophenol, 16.3 parts of 35% hydrochloric acid was added little by little under ice cooling, and 24.7 parts of a 20% aqueous sodium nitrite solution was dissolved. Was added and stirred for 2 hours to obtain a suspension containing a diazonium salt.

  Separately, 65 parts of water and 3 parts of sodium hydroxide were added to 19 parts of the pyrazolone compound represented by the formula (c-1), and then 100 parts of a 10% aqueous sodium acetate solution were added under ice cooling to give a pyrazolone compound (c -1) A solution was obtained.

  The following operations were performed under ice cooling. While stirring the pyrazolone compound (c-1) solution, the suspension containing the diazonium salt was added dropwise over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a dark solution. 20 parts of purified salt (sodium chloride) was added to the reaction solution and stirred for 1 hour. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 27.1 parts (yield 95%) of the azo compound represented by the formula (c-1-1).

  After 150 parts of water and 100 parts of dimethylformamide were added to and dissolved in 18.2 parts of the azo compound represented by the formula (c-1-1), 2.8 parts of chromium formate was added, and 5% at 100 ° C. A dark solution was obtained by heating for hours and stirring. After cooling to 25 ° C, 12 parts of a 20% aqueous sodium hydroxide solution was added, and after stirring for 30 minutes, 60 parts of purified salt (sodium chloride) was added to the reaction solution and stirred for 30 minutes. The dark solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 13.0 parts (yield 95%) of a chromium complex salt represented by the formula (d-1).

200 parts of methanol and 100 parts of dimethylformamide were added to 9.1 parts of the chromium complex salt represented by the formula (d-1) and dissolved, and then the compound represented by the formula (e-1) (Rhodamine 6G, Tokyo, Japan). 4.8 parts (made by Kasei Kogyo Co., Ltd.) were added and stirred for 30 minutes to obtain a dark red solution. Concentration at 50 ° C. under reduced pressure gave a dark solid.
To the obtained dark solid, 250 parts of water was added, and the dark solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain a compound represented by the formula (f-1) (hereinafter “metal complex dye A2-1-1a”). 10.6 parts (yield 76%).

Synthesis example 4
According to Example 2 of Unexamined-Japanese-Patent No. 2011-148995, the compound represented by Formula (c-2-1) was obtained. The structure of the compound represented by the formula (c-2-1) was confirmed by ¹ H-NMR (JMM-ECA-500; manufactured by JEOL Ltd.).
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ); 2.50 (2H, 2H, overlapped) 2.55 (3H, s), 3.51 (3H, s), 4.11 (2H, t), 4.23 (2H, t), 7.37 (1H, t), 7.74 (1H, t), 8.02 (1H, d), 8.03 (1H D), 15.6 (1H, s).

Next, after adding 93 parts of N-methylpyrrolidone to 3.7 parts of the compound represented by the formula (c-2-1) and heating to 80 ° C. to dissolve it, chromium formate n-hydrate 1.8 The mixture was added and stirred at 120 ° C. for about 7 hours to obtain a dark orange solution. This solution was poured into 210 parts of a 20% saline solution, and the resulting orange solid was filtered and dried under vacuum at 60 ° C., whereby 3.2 parts of the compound represented by the formula (d-2) ( Yield 82%). The compound represented by the formula (d-2) was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).
Ionization mode = ESI−: m / z = 960.0 [M−H] ⁻
Exact Mass: 961.2

A solution (s1) was prepared by adding 31.5 parts of N-methylpyrrolidone to 3.1 parts of the compound represented by the formula (d-2). Moreover, 15.4 parts of methanol was added to 1.6 parts of the compound represented by the formula (e-1) (Rhodamine 6G, manufactured by Tokyo Chemical Industry Co., Ltd.) to prepare a solution (t1). Thereafter, the solution (s1) and the solution (t1) were mixed at room temperature, stirred for about 1 hour, and poured into 430 parts of water. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure, and 3.4 parts of a compound represented by the formula (f-2) (hereinafter sometimes referred to as “metal complex dye A2-1-1b”) ( Yield 73%). The structure of the compound represented by the formula (f-2) was confirmed by elemental analysis (VARIO-EL; (Elemental Co., Ltd.)).
C64.7 H5.2 N10.8 Cr4.0

Synthesis example 5
After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-4-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of a 35% aqueous sodium nitrite solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve, followed by stirring for 2 hours. A suspension containing was obtained. Subsequently, an aqueous solution in which 5.6 parts of amidosulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water was slowly added to quench excess sodium nitrite.
Subsequently, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) is suspended in 70 parts of water, and the pH is adjusted to 8.0 using sodium hydroxide. did. The suspension containing the diazonium salt was added dropwise over 15 minutes while adding a 10% sodium hydroxide solution appropriately so that the pH was in the range of 7 to 7.5. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 11.7 parts (yield 87%) of the compound represented by the formula (c-3).

10 parts of the compound of the formula (c-3) are dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.), and ammonium sulfate (III) 12 water (manufactured by Wako Pure Chemical Industries, Ltd.) 3.1 After adding 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to reflux for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% brine, the reddish orange solid obtained after filtration was dried at 60 ° C., and 13.6 parts of the compound represented by formula (d-3) ( 63%). The structure of the compound represented by the formula (d-3) was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).
Ionization mode = ESI−: m / z = 882.1 [M−Na ⁺ ] ⁻
Exact Mass: 905.1

  18 parts of Rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd.), 170 parts of anhydrous chloroform (manufactured by Kanto Chemical Co., Ltd.), 1.0 part of camphorsulfonic acid (manufactured by Aldrich Co., Ltd.), 4- (N, N-dimethyl) Amino) pyridine (Tokyo Chemical Industry Co., Ltd.) 1.4 parts and triethylene glycol (Wako Pure Chemical Industries Co., Ltd.) 18 parts were added and stirred for about 30 minutes. Thereafter, 47 parts of anhydrous chloroform was added to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), and a solution dissolved beforehand was slowly added. Thereafter, the mixture was stirred at room temperature for about 2 hours. The liquid separation operation was performed twice with 150 parts of a 1N hydrochloric acid aqueous solution, and then the organic layer was washed twice with 150 parts of 10% saline. Next, 43 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes, and then the desiccant was filtered and the solvent was distilled off to obtain 20.6 parts (yield 90%) of the compound represented by the formula (e-2). It was.

The structure of the compound represented by the formula (e-2) was confirmed by mass spectrometry (LC: Agilent 1200 type, MASS: Agilent LC / MSD type).
Ionization mode = ESI +: m / z = 575.3 [M-Cl ⁻ ] ⁺
Exact Mass: 610.3

A solution (s2) was prepared by adding 4030 parts of methanol to 253 parts of the compound represented by the formula (d-3). Further, 1080 parts of methanol was added to 153 parts of the compound represented by the formula (e-2) to prepare a solution (t2). Thereafter, the solution (s2) and the solution (t2) were mixed at room temperature and stirred for about 1 hour. The resulting red solid was dried at 60 ° C. under reduced pressure, washed with 3500 parts of water, filtered, and dried at 60 ° C. under reduced pressure to obtain a compound represented by formula (f-3) (hereinafter “metal complex dye A2- 263 parts (yield 65%).
The structure of the compound represented by the formula (f-3) was confirmed by elemental analysis using an ICP emission spectrometer (ICPS-8100; manufactured by Shimadzu Corporation).
C55.6 H5.1 N11.9 Cr3.71

Synthesis Example 6
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 336 parts in a molar ratio of 50:50) was dissolved in 140 parts of ethyl lactate to prepare a solution, and this solution was kept at 70 ° C. for 4 hours using a dropping funnel. The solution was dropped into the flask.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight (Mw) was 8.0 × 10 ³ , the molecular weight distribution was 2.5, and the solid A resin B1 solution having a content of 48% and a solution acid value of 50 mg-KOH / g was obtained. The solid content acid value calculated from the solid content and the solution acid value is 104 mg-KOH / g. Resin B1 has the following structural units.

Synthesis example 7
333 parts of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the temperature of the solution in the flask was raised to 100 ° C., and then 18.7 parts of N-benzylmaleimide, 70.5 parts of benzyl methacrylate, 51.7 parts of methacrylic acid, 90.0 parts of methyl methacrylate, azobisisobutyro A mixture consisting of 5.2 parts of nitrile and 182 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours using a dropping funnel, and stirring was further continued at 100 ° C. for 5 hours after completion of the addition.
After the stirring, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with air. Then, 28.5 parts of glycidyl methacrylate, 1.3 parts of trisdimethylaminomethylphenol and 0.165 parts of hydroquinone were added. The reaction was continued at 110 ° C. for 6 hours to obtain a resin B2 solution having a solid content of 31%. Resin B2 had a weight average molecular weight (Mw) of 1.6 × 10 ⁴ and an acid value of 80 mg-KOH / g (in terms of solid content).

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

In Examples, the dyes listed in Table 1 were used as xanthene dyes, and the dyes listed in Table 2 were used as metal complex dyes. The maximum absorption wavelength (λ _max ) of each dye was determined as follows.

Measurement of maximum absorption wavelength (λ _max ) 0.35 g of dye was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to a volume of 100 cm ³ (concentration: 0.028 g / L) ), An ultraviolet visible near infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), an absorption spectrum at 400 to 700 nm was measured. From the absorption spectrum, the wavelength at which the absorbance is maximized was determined and set as the maximum absorption wavelength λ _max .

(Preparation of colored curable resin composition)
Examples 1-19
The following components were mixed to obtain a colored curable resin composition. The solvent (E) is mixed so that the solid content of the colored curable resin composition is 20%, and the surfactant (F) is contained in the colored curable resin composition in an amount of 0.01 mass. % To be mixed.
Dye (A): Dye described in Table 3 Resin (B): Resin B1 solution (solid content conversion) 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku ( 50 parts Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF) 15 parts Solvent (E): Ethyl lactate Surfactant (F); Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

Comparative Example 1
The following components were mixed to obtain a colored curable resin composition.
Dye: CI Solvent Red 130 9.500 parts Resin: Resin B2 solution (solid content conversion) 3.189 parts Polymerizable compound: Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) 784 parts Polymerization initiator: 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one 0.718 parts Polymerization initiator: 2,4-bis (trichloromethyl) -6-piperonyl- 1,3,5-triazine 0.558 parts Polymerization initiation aid: 4,4'-bis (diethylamino) benzophenone
0.239 parts Surfactant; Megafac (registered trademark) F475 (manufactured by DIC Corporation) 0.012 parts Solvent: propylene glycol monomethyl ether acetate 27.540 parts Solvent: propylene glycol monomethyl 53.460 parts

Comparative Example 2
A colored curable resin composition was obtained in the same manner as in Comparative Example 1 except that CI Solvent Red 130 was replaced with CI Solvent Red 125.

[Evaluation]
<Pattern preparation>
A colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then prebaked at 100 ° C. for 3 minutes. After standing to cool, the distance between the substrate coated with the colored curable resin composition and the quartz glass photomask is set to 80 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 200 mJ. Light was irradiated at an exposure dose of / cm ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. After light irradiation, the coating film was developed by immersing in a developer (aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide) at 23 ° C. for 80 seconds, washed with water, Inside, post-baking was performed at 220 ° C. for 20 minutes to obtain a pattern.

<Film thickness measurement>
The film thickness of the obtained pattern was measured using a film thickness measuring device (DEKTAK (registered trademark) 3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Tables 4 and 5.

<Evaluation of chromaticity and brightness>
About the obtained pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinates in the XYZ color system of CIE (Characteristic function of C light source) x, y) and the tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Tables 4 and 5.

<Preparation of coating film>
After applying the colored curable resin composition on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning) by spin coating so that the film thickness after post-baking is the same as the above pattern, 100 Pre-baked at 0 ° C. for 3 minutes. After standing to cool, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.), it was irradiated with light at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. After light irradiation, post-baking was performed in an oven at 220 ° C. for 20 minutes to obtain a coating film.

<Contrast evaluation>
About the obtained coating film, a contrast meter (CT-1; manufactured by Aisaka Electric Co., Ltd., color / color difference meter BM-5A; manufactured by Topcon Corporation, light source: F-10, polarizing film; manufactured by Aisaka Electric Co., Ltd.) Was used to measure the contrast. In addition, the blank value at the time of a measurement is 10000 in Examples 1-17, and 30000 in Examples 18 and 19. The results are shown in Tables 4 and 5.

<Heat resistance evaluation>
The obtained coating film was heated in an oven at 230 ° C. for 2 hours. The xy chromaticity coordinates (x, y) and Y are measured before and after heating, and the color difference ΔEab * is calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). Are shown in Table 6. ΔEab * means that the smaller the color change, the smaller the color change. If ΔEab * is 10 or less, it can be said that the coating film has no practical problem as a color filter. Moreover, if the heat resistance of a coating film is favorable, it can be said that the heat resistance of the pattern produced from the same colored curable resin composition is also favorable.

<Light resistance evaluation>
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is disposed on the obtained coating film, and a light resistance tester (Suntest CPS +: manufactured by Toyo Seiki Co., Ltd.). Xenon lamp light was irradiated for 48 hours.
The xy chromaticity coordinates (x, y) and Y are measured before and after the irradiation, and the color difference ΔEab * is calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). Are shown in Table 6. ΔEab * means that the smaller the color change, the smaller the color change. If ΔEab * is 10 or less, it can be said that the coating film has no practical problem as a color filter. Moreover, if the light resistance of a coating film is favorable, it can be said that the light resistance of the pattern produced from the same colored curable resin composition is also favorable.

  From the above results, it was confirmed that the pattern formed from the colored curable resin composition of the present invention was excellent in brightness. From this, it can be seen that according to the colored curable resin composition of the present invention, a color filter having excellent color performance can be produced.

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

Claims (7)

Including a colorant, a binder resin, a polymerizable compound and a polymerization initiator,
A colored curable resin composition, wherein the colorant is a colorant comprising a xanthene dye (A1) and a metal complex dye (A2). 2. The metal complex dye (A2) is at least one selected from the group consisting of a compound represented by formula (3), a compound represented by formula (4), and a compound represented by formula (6). The colored curable resin composition as described.

[In the formula (3), R ^{31 to} R ⁴⁸ each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁵¹ , —SO ₃ H or — Represents SO ₂ CH ₃ .
R ⁴⁹ and R ⁵⁰ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁵¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ^{1 to} A ⁴ each independently represent * —O—, * —O—CO—, or * —CO—O—. * Represents a bond with M.
M represents Cr or Co.
n represents an integer of 1 to 5.
D ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]

[In the formula (4), R ^{52 to} R ⁶⁰ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, —SO ₂ NHR ⁶² , —SO ₃ H or It represents a -SO ₂ CH _3.
R ⁶¹ each independently represents a hydrogen atom, a methyl group or an ethyl group.
R ⁶² each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 2 to 15 carbon atoms.
A ⁵ and A ⁶ each independently represent * —O—, * —O—CO— or * —CO—O—.
* Represents a bond with M1.
M1 represents Cr or Co.
n1 represents the integer of 0-2.
D1 ⁺ represents a monovalent cation derived from hydrone, a monovalent metal cation or a compound having a xanthene skeleton. ]
Wherein (6), R ⁸¹ represents a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, hydrogen atoms contained in the saturated hydrocarbon ^{group, -OH, -OR 88, -CO-} OR ^{88, -O-COR 88, -CONR} 88 R 89, may be substituted by a monovalent aromatic hydrocarbon group, or a halogen atom having 6 to 10 carbon atoms, -CH ₂ contained in the saturated hydrocarbon group -May be replaced by at least one of -O- and -CO-.
R ⁸² represents a hydrogen atom, -CN, or -CONH _2.
R ⁸³ represents an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom.
R ⁸⁴ to R ^87, independently of one ^{another, -R 88, -OR 88, -CO} -OR 88, -COR 88, -OCO-OR 88, -O-COR 88, -CN, -NO 2, a halogen atom represents _{-SO 3 H, -SO 3 Na,} -SO 3 K, -SO 2 NR 88 R 89 or -NR ⁹¹ R ^92. R ⁸⁴ and R ⁸⁵ , R ⁸⁵ and R ⁸⁶ , and R ⁸⁶ and R ⁸⁷ may be bonded to each other to form a 6 to 7 membered ring containing carbon of a benzene ring.
R ⁸⁸ and R ⁸⁹ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or a monovalent aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon group, and a hydrogen atom contained in the aliphatic hydrocarbon group, the aralkyl group and the aromatic hydrocarbon group may be substituted with —OR ⁹⁰ .
R ⁹⁰ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ⁹¹ and R ⁹² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, an acyl group having 2 to 8 carbon atoms, or a tetrahydrofurfuryl group. R ⁹¹ and R ⁹² may combine with each other to form a ring containing a nitrogen atom.
A ^{11 to} A ¹⁴ each independently represent * —O—, * —O—CO— or * —CO—O—. * Represents a bond with M ² .
M ² represents Cr or Co.
n2 represents an integer of 1 to 5.
D2 ⁺ represents a monovalent cation derived from a compound having a hydrone, a monovalent metal cation or a xanthene skeleton. ]   The colored curable resin composition according to claim 1 or 2, wherein the metal complex dye (A2) is a dye containing a metal complex dye (A2-1) having a maximum absorption wavelength in the range of 490 nm to 580 nm.   The ratio (A1: A2) between the content of the xanthene dye (A1) and the content of the metal complex dye (A2) is 1:99 to 99: 1 on a mass basis. The colored curable resin composition according to one item.   The colored curable resin composition according to any one of claims 1 to 4, wherein the polymerization initiator is a polymerization initiator containing an oxime compound.   The color filter formed with the colored curable resin composition as described in any one of Claims 1-5.   A display device comprising the color filter according to claim 6.