JP5866955B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a colored curable resin composition.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a colored curable resin composition, C.I. I. Pigment green 7 and C.I. I. A colored curable resin composition containing only Pigment Yellow 138 is known (for example, Patent Document 1).

JP 2009-265641 A

  When the above-mentioned colored curable resin composition known from the past produces a bluish green color filter from the composition, the brightness of the color filter may not always be satisfactory.

The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant is a colorant comprising a chlorinated copper phthalocyanine pigment and a yellow dye,
A colored curable resin composition having a yellow dye content of 1% by mass to 65% by mass with respect to the total amount of the colorant.
[2] A chlorinated copper phthalocyanine pigment is C.I. I. The colored curable resin composition according to [1], which is CI Pigment Green 7.
[3] A color filter formed from the colored curable resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

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

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is a chlorinated copper phthalocyanine. A pigment (hereinafter sometimes referred to as “pigment (P)”) and a yellow dye (hereinafter sometimes referred to as “yellow dye (Y)”).
By using the colorant (A) containing the yellow dye (Y) and the pigment (P), the brightness of the color filter is improved.
The colored curable resin composition of the present invention preferably further contains a solvent (E).
Moreover, the colored curable resin composition of this invention may also contain at least 1 sort (s) chosen from the group which consists of a polymerization initiator (D1) and surfactant (F) as needed.
In addition, in this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The colorant (A) includes the pigment (P) and the yellow dye (Y), and may further include a pigment different from the pigment (P) (hereinafter sometimes referred to as “pigment (A2)”).

［式（Ｐ１）中、ａ１、ａ２、ａ３及びａ４は、互いに独立に、０〜４の整数を表し、（ａ１＋ａ２＋ａ３＋ａ４）は１０以上１６以下である。］
で表される化合物を含む顔料であることが好ましい。顔料（Ｐ）中、式（Ｐ１）で表される化合物の含有量は５０質量％以上が好ましく、より好ましくは７０質量％以上、さらに好ましくは９０質量％以上である。 The pigment (P) has the formula (P1)

[In Formula (P1), a1, a2, a3 and a4 each independently represent an integer of 0 to 4, and (a1 + a2 + a3 + a4) is 10 or more and 16 or less. ]
It is preferable that it is a pigment containing the compound represented by these. In the pigment (P), the content of the compound represented by the formula (P1) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more.

  (A1 + a2 + a3 + a4) is preferably 13 or more and 16 or less, and more preferably 14 or more and 16 or less.

  Examples of the pigment (P) include C.I. I. And CI Pigment Green 7.

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

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

  The content of the pigment (P) is preferably 1% by mass to 99% by mass, more preferably 35% by mass to 99% by mass, and more preferably 40% by mass to 98% by mass with respect to the total amount of the colorant (A). The following is more preferable.

The yellow dye (Y) preferably has a maximum absorption wavelength in the range of 400 nm to 480 nm, more preferably in the range of 400 nm to 450 nm, and still more preferably in the range of 410 nm to 435 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.
Examples of yellow dyes (Y) include dyes classified as yellow dyes in the Color Index (published by The Society of Dyers and Colorists). Examples of chemical structures include azo dyes, metal complex dyes, quinoline dyes, and acridines. Examples include dyes, anthraquinone dyes, naphthalimide dyes, nitro dyes, methine dyes, cyanine dyes, and triphenylmethane dyes.
Examples of the yellow dye (Y) include C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 13, 14, 15, 19, 21, 23, 24, 25, 25: 1, 38, 62 63, 68, 79, 81, 82, 83, 83: 1, 88, 89, 90, 94, 98, 99, 151, 161, 162;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 59, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 121, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; and the like.

  Among these, as the yellow dye (Y), a yellow azo dye is preferable. For example, JP 2009-13112 A, JP 2009-13290 A, JP 2009-13291 A, JP 2009-13292 A, JP 2009-13293 A, JP 2009-280691 A, JP 2009-299030 A, JP 2010-1469 A, JP 2010-275531 A, JP 2010-275532 A, JP A. The dye containing the compound described in 2010-275533 gazette is mentioned.

  The yellow azo dye is more preferably a dye containing a compound represented by the formula (1).

Wherein (1), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.
B ⁰ represents a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent. Represent.
R ⁵¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or an acyl group having 2 to 18 carbon atoms which may have a substituent.
p1 represents 1 or 2. When p1 is 2, the plurality of A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same as or different from each other.
When p1 is 1, R ⁵² represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. When p1 is 2, R ⁵² is Represents a C1-C35 divalent saturated hydrocarbon group which may have a substituent, and —CH ₂ — contained in the monovalent saturated hydrocarbon group and the divalent saturated hydrocarbon group is , -O-, -S-, -CO- and -NR'- may be substituted.
R ′ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. ]

  The compound represented by the formula (1) is preferably a compound represented by the formula (2).

Wherein ^(2), Z 1, ^{Z 2} and ^{Z 3} each independently represents a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a ^{substituent, Z} 1, —CH ₂ — contained in Z ² and Z ³ may be replaced by —CO— or —O—.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon group which may have a substituent. Represents 2-18 acyl groups.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. Represents a monovalent heterocyclic group. ]

Z ¹ , Z ² and Z ³ each independently represent a C 1-16 divalent aliphatic hydrocarbon group which may have a substituent. Carbon number of a substituent is not contained in carbon number of a C1-C16 bivalent aliphatic hydrocarbon group, The number becomes like this. Preferably it is 2-10, More preferably, it is 2-8.
Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include alkanediyl groups having 1 to 16 carbon atoms, such as methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, Examples include a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.
—CH ₂ — contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be replaced by —CO— or —O—. The hydrogen atom contained in the aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

Z ¹ and Z ² are preferably an alkanediyl group having 1 to 8 carbon atoms which may contain —O—, and an alkanediyl group having 5 to 7 carbon atoms which may contain —O—. More preferably. Preferable groups include, for example, — (CH ₂ ) ₃ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O— (CH _{2) 2} - or _-CH 2 -CH (CH ₃₎ - and the like.
Z ³ is preferably a C 1-8 divalent aliphatic hydrocarbon group which may contain —C (═C) —, and is an unsubstituted alkanediyl group having 1 to 8 carbon atoms. More preferably, it is an unsubstituted alkanediyl group having 4 to 8 carbon atoms. Preferable groups include, for example, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, or —CH ₂ —C (═CH ₂ ) —.

The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms representing R ⁵¹ , R ⁵² , R ^53, and R ⁵⁴ may be linear, branched, or cyclic. The carbon number of the saturated hydrocarbon group does not include the carbon number of the substituent, preferably 6 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), methylhexyl group (1,5-dimethylhexyl group, etc.), ethylhexyl group (2-ethylhexyl group, etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl Groups (such as 2-methylcyclohexyl group) and cyclohexylalkyl groups.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (such as 3- (isopropoxy) propyl group) and an alkoxypropyl group (3- (2-ethylhexyloxy) propyl group, etc.). Examples of the C1-C16 aliphatic hydrocarbon group substituted with a carboxy group include a 2- (carboxy) ethyl group, a 3- (carboxy) propyl group, and a 4- (carboxy) butyl group.

The divalent saturated hydrocarbon group having 1 to 35 carbon atoms representing R ⁵² may be any of linear, branched or cyclic, methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group. , Hexanediyl group, heptanediyl group, octanediyl group, decandidiyl group, tetradecandiyl group, hexadecandiyl group, cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group, cycloheptanediyl group, cyclooctanediyl Group, cyclodecanediyl group, cyclotetradecanediyl group, cyclohexadecanediyl group, adamantanediyl group and the like. Of these, a linear or branched chain is preferable.
—CH ₂ — contained in the divalent saturated hydrocarbon group having 1 to 35 carbon atoms may be replaced by —O—, —S—, —CO— or —NR′—. The hydrogen atom contained in the C1-C35 divalent saturated hydrocarbon group may be substituted with a halogen atom such as a fluorine atom.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms representing R ′ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.

A hydrogen atom contained in an acyl group having 2 to 18 carbon atoms representing R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted with an alkoxy group having 1 to 8 carbon atoms. The carbon number of the acyl group having 2 to 18 carbon atoms which may have a substituent is counted including the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the acyl group that may have a substituent include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ⁵³ and R ⁵⁴ are preferably a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms. Preferable groups include, for example, a hydrogen atom, an acetyl group, or a propionyl group.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms representing A ⁰ , A ¹ and A ² include a phenylene group and a naphthalenediyl group, and among them, a phenylene group is preferable.

Examples of the substituent for the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, and N-substituted sulfamoyl groups and the like can be mentioned.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, or a bromine atom is preferable.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

Examples of N-substituted sulfamoyl groups include N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N- Isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1, 1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) ) Sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamo Group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.
The N-substituted sulfamoyl group preferably has 1 to 16 carbon atoms, more preferably 4 to 16 carbon atoms.

［Ｒは、水素原子又は有機基を表す。］
該有機基としては、例えば、後述のＲ^５９と同様の基が挙げられる。 B ⁰ , B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or 3 carbon atoms which may have a substituent. Represents a monovalent heterocyclic group of -14.
Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.
Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or an organic group. ]
Examples of the organic group include the same groups as R ⁵⁹ described below.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms is a hydroxy group, an oxo group, or a monovalent fatty acid having 1 to 16 carbon atoms. May be substituted with an aromatic hydrocarbon group, a cyano group, an amino group or an N-substituted amino group.
As the N-substituted amino group, —NHR ⁵⁷ group or —NR ⁵⁷ R ⁵⁸ group is preferable. However, R ⁵⁷ and R ⁵⁸ are each independently a number monovalent saturated hydrocarbon group or may have a substituent group of carbon atoms of 1 to 16 carbon atoms which may have a substituent 3-14 Represents a monovalent heterocyclic group. Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

B ¹ and B ² are preferably the same type of group, and more preferably A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are the same type of group, respectively. When these groups are used, it is easy to produce the compound represented by the formula (2).

［式（２−ａ）中、Ｒ^５９は水素原子又は置換基を有していてもよい炭素数１〜１６の１価の飽和炭化水素基を表す。Ｒ^６０は、置換基を有していてもよい炭素数１〜１６の１価の飽和炭化水素基を表す。］
式（１）で表される化合物及び式（２）で表される化合物が式（２−ａ）で表される基を含む場合、これらはその互変異性体も含む。 B ⁰ , B ¹ and B ² are preferably each independently a group represented by the formula (2-a).

[In the formula (2-a), R ⁵⁹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. ]
When the compound represented by the formula (1) and the compound represented by the formula (2) include a group represented by the formula (2-a), these also include tautomers thereof.

Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms include the same ones as described above. R ⁵⁹ is a methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), a methylhexyl group (such as 1,5-dimethylhexyl group), an ethylhexyl group (such as 2-ethylhexyl group), A branched aliphatic hydrocarbon group such as a methylcyclohexyl group (such as 2-methylcyclohexyl group) and an alkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group) is preferable.
Examples of the substituent for R ⁵⁹ and R ⁶⁰ include a hydroxy group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms, and an acyloxy group having 1 to 8 carbon atoms. Examples of the alkoxy group having 1 to 8 carbon atoms include the same ones as described above. Examples of the acyloxy group having 1 to 8 carbon atoms include acetyloxy group, propionyloxy group, hexylcarbonyloxy group, octylcarbonyloxy group, benzoyloxy group and the like.
R ⁶⁰ is preferably a methyl group.

As a compound represented by Formula (1), the compound described in Unexamined-Japanese-Patent No. 2010-275531 is mentioned, Preferably the compound represented by Formula (1-1)-Formula (1-10) is mentioned. It is done. A ¹ , A ² , Z ^1, and Z ² in the table represent a bond in which the right bond is closer to Z ³ .

  The compound represented by Formula (2) can be manufactured by the method described in Unexamined-Japanese-Patent No. 2010-275531.

  Content of yellow dye (Y) is 1 mass% or more and 65 mass% or less with respect to the total amount of a coloring agent (A), and 2 mass% or more and 55 mass% or less are preferable.

The colorant (A) may further contain the pigment (A2) together with the pigment (P) and the yellow dye (Y).
Examples of the pigment (A2) include compounds classified as pigments according to a color index (published by The Society of Dyers and Colorists). Among these, yellow pigments and green pigments are preferable.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like, and yellow pigments described in JP-A Nos. 2001-354869 and 2007-224176.
Examples of green pigments include C.I. I. Pigment green 36, 58 and the like.

  Among these, as the pigment (A2), C.I. I. Pigment yellow 138, 139, 150; I. Pigment Green 36 and 58 are 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.

Pigment (A2) is optionally treated with rosin, surface treatment using a pigment derivative having an acidic group or basic group introduced, grafting onto the pigment surface with a polymer compound, sulfuric acid atomization method, etc. May be subjected to the atomization treatment by, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like.
The pigment (A2) preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained. The pigment (P) and the pigment (A2) may be mixed and then dispersed together.

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

  When the pigment (A2) 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.

When the colorant (A) is composed of the pigment (P) and the yellow dye (Y), these contents are respectively based on the total amount of the colorant (A).
Pigment (P): 35% by mass or more and 99% by mass or less Yellow dye (Y): 1% by mass or more and 65% by mass or less are preferable,
Pigment (P); 40 mass% or more and 98 mass% or less Yellow dye (Y); 2 mass% or more and 55 mass% or less are more preferable.

When the colorant (A) contains the pigment (A2), the contents of the pigment (P), the yellow dye (Y), and the pigment (A2) are each based on the total amount of the colorant (A),
Pigment (P): 5% by mass or more and 98% by mass or less Yellow dye (Y): 1% by mass or more and 65% by mass or less Pigment (A2); 1% by mass or more and 90% by mass or less are preferable,
Pigment (P): 9% by mass or more and 97% by mass or less Yellow dye (Y): 2% by mass or more and 55% by mass or less Pigment (A2): 1% by mass or more and 85% by mass or less is more preferable.

  The content of the colorant (A) is preferably 5% by mass to 70% by mass, more preferably 8% by mass to 60% by mass with respect to the solid content in the colored curable resin composition. Preferably it is 10 mass%-57 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 a resin or a polymerizable compound can be contained in the composition. Therefore, a pattern with sufficient mechanical strength can be formed.

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

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.
In the present specification, “(meth) acryloyl” represents at least one selected from the group consisting of acryloyl and methacryloyl. Notations such as “(meth) acrylic acid” and “(meth) acrylate” have the same meaning.

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

  Examples of (b) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) is, for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an unsaturated alicyclic 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, and m-vinylbenzyl glycidyl ether. P-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) ) Styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) ) Styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6 -Tris (glycidyloxymethyl) styrene etc. are mentioned.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth). Acrylate (for example, Cyclomer A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) And a compound represented by the formula (II).

[In Formula (I) and Formula (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 represents a -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 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^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 include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— or * —CH ₂ CH ₂ —O—, more preferably a single bond or * —CH ₂ CH. ₂ -O- (* represents a bond with O).

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

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

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or as a mixture in any ratio. When used as a mixture, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

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

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

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

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

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

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

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units constituting the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming the colored pattern, and the solvent resistance of the resulting colored pattern, There is a tendency to be excellent in heat resistance and mechanical strength.

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

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

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

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

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (c); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10 to 90 mol%
It is more preferable that

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

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / vinyl toluene / dicyclopentenyl (meth) acrylate Polymer, resin such as 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, Resin [K3] such as styrene / (meth) acrylic acid copolymer; resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / Styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) Resin such as acrylate-added resin [K4]; Tricyclodecyl (meth) acrylate / g Residue obtained by reacting (meth) acrylic acid with a copolymer of sidyl (meth) acrylate, and (meth) acrylic acid reacted with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resin [K5]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further reacting with tetrahydrophthalic anhydride Resin [K6] etc. are mentioned.

  Especially, as resin (B), resin [K1], resin [K2], and resin [K3] are preferable.

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

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

  Content of resin (B) 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, it is 17-55 mass. %. When content of resin (B) exists in the said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

<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) by the action of light or heat, and includes, for example, a polymerizable ethylenically unsaturated bond. The compound etc. which have are mentioned, Preferably a (meth) acrylic acid ester compound is mentioned.

  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.

  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, the curing is sufficiently performed, the film thickness ratio before and after the development is improved, the pattern is less likely to be undercut, and the adhesion is good. It is preferable because it tends to become.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used.

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

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Thenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

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

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

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

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and O-acyloxy compounds. More preferred is a polymerization initiator containing an oxime compound, and more preferred is a polymerization initiator containing an O-acyloxime compound and an alkylphenone compound.

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

In addition to the polymerization initiator (D), a polymerization initiation assistant (D1) may further be included. The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the photopolymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

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

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds include 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.

As the polymerization initiation assistant (D1), a thioxanthone compound is preferable.
Moreover, when using a polymerization start adjuvant (D1), the usage-amount becomes with respect to the total amount of 100 mass parts of resin (B) and polymeric compound (C), Preferably it is 0.1-30 mass parts. 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.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, ester solvents (solvents containing —COO—), ether solvents other than ester solvents (solvents containing —O—), ether ester solvents (solvents containing —COO— and —O—), ketones other than ester solvents A solvent (solvent containing —CO—), an alcohol solvent, an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide, or the like can be selected and 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.

  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.

<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.

  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.

<Other ingredients>
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.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a polymerization initiation auxiliary agent used as necessary ( D1), the solvent (E), the surfactant (F) and other components can be mixed.
The pigment (P) is preferably mixed with the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. In the obtained pigment dispersion, the yellow dye (Y), the remainder of the resin (B) and the polymerizable compound (C), and the polymerization initiator (D) and the remainder of the solvent (E) used as necessary The desired colored curable resin composition can be prepared by mixing the surfactant (F) and other components so as to have a predetermined concentration.
The yellow dye (Y) may be preliminarily dissolved in 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 prepared by mixing as described above is preferably filtered with a filter having a pore size of about 0.1 to 10 μm.

<Color filter>
The colored curable resin composition of the present invention is useful for producing a bluish green color filter. The bluish green color filter has, for example, a C light source and CIE chromaticity coordinates in a 2-degree field of view preferably in the range of 0.140 ≦ x ≦ 0.270, 0.500 ≦ y ≦ 0.690, more preferably 0. In the range of 170 ≦ x ≦ 0.260 and 0.500 ≦ y ≦ 0.680, more preferably in the range of 0.200 ≦ x ≦ 0.250 and 0.550 ≦ y ≦ 0.680, high brightness A bluish green color filter can be obtained.
Examples of the method for producing the color pattern of the color filter from the colored curable resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the composition layer can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm. .

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

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.

30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 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 composition layer is not particularly limited, and can be appropriately adjusted according to the film thickness of the target color filter.

Next, the composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
It is preferable to use an exposure apparatus such as a mask aligner and a stepper because the entire exposure surface can be irradiated with parallel rays uniformly and accurate alignment between the photomask and the substrate can be performed.

By developing the exposed composition layer in contact with a developer, a colored pattern is formed on the substrate. By the development, the unexposed portion of the composition layer is dissolved and removed 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 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, it is preferable to post-bake the obtained colored pattern. 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.

The colored pattern and the colored coating film thus obtained are useful as a color filter.
According to the colored curable resin composition of the present invention, it is possible to produce a green color filter with a particularly high bluishness. Therefore, the color filter is a display device (for example, a liquid crystal display device, an organic EL device, etc.). It is useful as a color filter used for electronic paper, solid-state imaging devices and the like.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

Synthesis example 1
200 parts of water was added to 10 parts of m-toluidine-4-sulfonic acid (compound represented by formula (a-2)), and then adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. After adding 39 parts of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution obtained by dissolving 10.1 parts of amidosulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  14 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one (a compound represented by the formula (c-2)), 125 parts of water and 25 parts of N-methylpyrrolidone After adding a portion, the mixture was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and then the suspension containing the diazonium salt was added dropwise by a pump over 2 hours while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 21.4 parts (yield 87%) of the compound represented by the formula (d-3).

Compound (d-3) 0.35 g was dissolved in N, N-dimethylformamide to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 433 nm.

  Into a flask equipped with a condenser and a stirrer, 5.0 parts of compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were added, while maintaining at 20 ° C. or lower with stirring. 2.4 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C., the reaction was continued for 2 hours at the same temperature, and then cooled to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring and then stirred for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried under reduced pressure at 60 ° C. for 2 hours. Prepare a flask equipped with a condenser and a stirrer separately, add 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone, and adjust in advance while maintaining the temperature at 20 ° C. or lower with stirring. The yellow crystals obtained were added over 1 hour. After adding the yellow crystals, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, this mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 3.9 parts (yield 69%) of the compound represented by the formula (III-3).

Compound (III-3) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L). The absorption spectrum was measured using a photometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 431 nm.

  The following reaction was performed in a nitrogen atmosphere. 150 parts of N-methylpyrrolidone was added to 49.9 parts of compound (III-3), and then stirred for 30 minutes to prepare a reaction solution. While stirring the reaction solution at room temperature, 6.8 parts of sebacic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. 7.8 parts of adipic acid chloride was added dropwise. After completion of dropping, the mixture was further stirred for 8 hours. After pouring the reaction solution into 300 parts of water, 80 parts of ethyl acetate was added and stirred for 30 minutes. The organic phase was separated using a separatory funnel, and further washed with 500 parts of water, 3000 parts of a 10% aqueous sodium carbonate solution, 1000 parts of an aqueous 10% acetic acid solution, and 1000 parts of ion-exchanged water. The separated organic phase was evaporated to obtain 2.0 parts of dye (I), which is a mixture of the compound represented by formula (1-6) and the compound represented by formula (1-7). It was. Yield 85%.

Dissolve 0.35 g of dye (I) in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), spectrophotometer The absorption spectrum was measured using (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.2 (arbitrary unit) at λmax = 431 nm.

<Measurement of content ratio in mixture>
The content ratio of the compound represented by the formula (1-6) and the compound represented by the formula (1-7) in the dye (I) is determined by a calibration curve method using high performance liquid chromatography (HPLC). It was measured. The calibration curve method is a method for determining an unknown concentration from the concentration-absorbance relationship of a standard solution row of a known concentration when determining the concentration of a substance in a solution.

HPLC system Prominence (manufactured by Shimadzu Corporation)
Liquid feeding unit: Two LC-20AT
Autosampler: One SIL-20A
Column oven: One CTO-20A
UV detector: One SPD-20A
Online degasser: DGU-20A single column Wakosil II 3C18HG (3μm, 3mmφ × 150mm)
Mobile phase A solution: 0.1% TBAB / water: acetonitrile (9: 1)
Liquid B: 0.1% TBAB / water: acetonitrile (1: 9)
Gradient (liquid B)
B initial concentration 25%
25% → (30 minutes) → 100% (20 minutes hold)
Detection wavelength 254nm
Column temperature 40 ° C
Flow rate 0.5mL / min
Injection volume 5μL
TBAB: Tetrabutylammonium bromide

  The compound represented by the formula (1-6) and the compound represented by the formula (1-7) were each dissolved in acetonitrile to prepare a solution having a concentration described in Table 11. The solution was subjected to high performance liquid chromatography analysis under the above conditions, and the elution time and peak area were measured. The results are shown in Table 11.

From the concentration of the solution and the measured peak area, a calibration curve was obtained as the following equation.
Calibration curve of the compound represented by formula (1-6): (peak area) = 72.2 × (concentration)
Calibration curve of the compound represented by formula (1-7): (peak area) = 76.0 × (concentration)

Dye (I) 13.9 mg was dissolved in acetonitrile, the volume was adjusted to 50 cm ³ (concentration: 0.278 g / L), high performance liquid chromatography analysis was performed under the above conditions, and elution time and peak area were measured. The compound represented by formula (1-7) was eluted at an elution time of 35.9 minutes, and the peak area was 944436. The compound represented by formula (1-6) was eluted at an elution time of 37.9 minutes, and the peak area was 1108707.
Using the above calibration curve, the content ratio of each compound in the dye (I) was determined. As a result, the compound represented by the formula (1-6) / the compound represented by the formula (1-7) = 44 7 / 55.3.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０質量部を乳酸エチル２２５質量部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗは、９．１×１０^３、分子量分布は２．１、固形分２６質量％、固形分酸価１２０ｍｇ−ＫＯＨ／ｇの樹脂Ｂ１溶液を得た。樹脂Ｂ１は、下記の構造単位を有する。 Synthesis example 2
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 305 parts by mass of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 60 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) The compound to be mixed is mixed at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts by mass and 140 parts by mass of ethyl lactate, and the solution is added using a dropping funnel over 4 hours. It was dripped in the flask kept at 70 degreeC.

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

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

Example 1
(Preparation of colored curable resin composition)
(A) Colorant: C.I. I. Pigment Green 7 (pigment) 38 parts Acrylic pigment dispersant 17 parts Propylene glycol monomethyl ether acetate 245 parts are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: Dye (I) (Yellow dye) 38 parts (B) Resin: Resin B1 (solid content conversion) 40 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad DPHA; Nippon Kayaku ( 60 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF)
10 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts (E) Solvent: 261 parts of ethyl lactate (E) Solvent: Propylene glycol monomethyl ether acetate A colored curable resin composition was obtained by mixing 424 parts.

[Preparation of colored pattern]
The colored curable resin composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a composition layer. After cooling, the distance between the substrate on which the composition layer is formed and the quartz glass photomask is set to 200 μm, and exposure is performed at 40 mJ / cm ^{2 in} an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Light was irradiated in an amount (based on 365 nm). A photomask having a 100 μm line and space pattern was used. The composition layer after the light irradiation was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds, washed with water, A colored pattern was obtained by post-baking at 20 ° C. for 20 minutes.

[Film thickness measurement]
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 12.

[Chromaticity evaluation]
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and brightness Y were measured. The results are shown in Table 12.

Example 2
(A) Colorant: C.I. I. Pigment Green 7 (pigment) 43 parts Acrylic pigment dispersant 19 parts Propylene glycol monomethyl ether acetate 272 parts are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: C.I. I. Pigment Yellow 138 (pigment) 17 parts Acrylic pigment dispersant 5.1 parts Propylene glycol monomethyl ether acetate 86 parts are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: Dye (I) (Yellow dye) 26 parts (B) Resin: Resin B1 (solid content conversion) 40 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad DPHA; Nippon Kayaku ( 60 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF)
10 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.13 parts (E) Solvent: 256 parts of ethyl lactate (E) Solvent: Propylene glycol monomethyl ether acetate A colored curable resin composition was obtained by mixing 386 parts.
A colored pattern was prepared by the same operation as in Example 1, and film thickness measurement and chromaticity evaluation were performed. The results are shown in Table 12.

Example 3
(Preparation of colored curable resin composition)
(A) Colorant: C.I. I. Pigment Green 7 (pigment) 44 parts Acrylic pigment dispersant 20 parts Propylene glycol monomethyl ether acetate 273 parts are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: C.I. I. Pigment Yellow 138 (pigment) 26 parts Acrylic Pigment Dispersant 7.8 parts Propylene Glycol Monomethyl Ether Acetate 129 parts are mixed, and a pigment dispersion in which the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: Dye (I) (Yellow dye) 18 parts (B) Resin: Resin B1 (solid content conversion) 40 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad DPHA; Nippon Kayaku ( 60 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure OXE 01; manufactured by BASF)
10 parts (F) Leveling agent: Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.14 parts (E) Solvent: 252 parts of ethyl lactate (E) Solvent: Propylene glycol monomethyl ether acetate A colored curable resin composition was obtained by mixing 353 parts.
A colored pattern was prepared by the same operation as in Example 1, and film thickness measurement and chromaticity evaluation were performed. The results are shown in Table 12.

Comparative Example 1
Colorant: C.I. I. Pigment Green 7 (pigment) 7.5 parts Colorant: C.I. I. Pigment Yellow 138 (pigment) 7.5 parts Pigment dispersant 6 parts Solvent: Propylene glycol monomethyl ether acetate 25 parts Solvent: Ethyl 3-ethoxypropionate 11 parts mixed and dispersed,
Resin: Copolymer of benzyl methacrylate / methacrylic acid = 70/30 (molar ratio) (acid value is 113; weight average molecular weight in terms of polystyrene is 30,000) 28 parts Polymerizable compound: dipentaerythritol hexaacrylate 8 parts Polymerization start Agent: Irgacure 907 (manufactured by BASF) 2 parts Surfactant: Megafac F477 (manufactured by DIC Corporation) 2 parts Solvent: 126 parts of propylene glycol monomethyl ether acetate Solvent: 54 parts of ethyl 3-ethoxypropionate A colored curable resin composition was obtained.

[Production and evaluation of colored coating film]
The colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle XG; manufactured by Corning), and then prebaked at 100 ° 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 at 220 ° C. for 20 minutes in an oven to obtain a colored coating film.
About the obtained colored coating film, it carried out similarly to Example 1, and performed film thickness measurement and chromaticity evaluation. The results are shown in Table 12.

  From the above results, it was confirmed that the colored pattern formed from the colored curable resin composition of the present invention was excellent in lightness. From this, it is understood that a display device having excellent color performance can be produced by using a color pattern formed from the colored curable resin composition of the present invention as a color filter.

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

Claims (4)

Including a colorant, a resin, a polymerizable compound and a polymerization initiator,
The colorant is a colorant comprising a chlorinated copper phthalocyanine pigment and a yellow dye,
The yellow dye is a compound represented by the formula (2),
A colored curable resin composition having a yellow dye content of 1% by mass to 65% by mass with respect to the total amount of the colorant.

Wherein ^(2), Z 1, ^{Z 2} and ^{Z 3} each independently represents a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a ^{substituent, Z} 1, —CH ₂ — contained in Z ² and Z ³ may be replaced by —CO— or —O—.
R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon group which may have a substituent. Represents 2-18 acyl groups.
A ¹ and A ² each independently represent a C 6-14 divalent aromatic hydrocarbon group which may have a substituent.
B ¹ and B ² are each independently a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a C ^{3 to} 14 carbon group which may have a substituent. Represents a monovalent heterocyclic group. ]
  Chlorinated copper phthalocyanine pigments are C.I. I. The colored curable resin composition according to claim 1, which is CI Pigment Green 7.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 3.