TW201331711A - Colored curable resin composition - Google Patents

Abstract

Provided is colored curable resin composition, comprising a coloring agent, a resin, a polymerizable compound and a polymerizing initiator, wherein the coloring agent contains a copper chloride phthalocyanine pigment and a yellow dye, the amount of the yellow dye is between 1% by mass and 65% by mass based on the total amount of the coloring agent. A colored curable resin composition useful for the manufacture of a green color filter being tinged with blue in a high lightness is provided in the present invention.

Description

Colored curable resin composition

The present invention relates to a color hardening resin composition.

The colored curable resin composition is a color filter used for a display device such as a liquid crystal display panel, an electroluminescence panel, or a plasma display panel. In the colored curing resin composition, a coloring curable dendritic composition containing only C.I. Pigment Green 7 and C.I. Pigment Yellow 138 is known as a coloring agent (for example, JP 2009-265641-A).

In the case of the above-described colored curable resin composition, when the blue color green color filter is produced from the composition, the brightness of the color filter may not be sufficiently satisfied.

The present invention includes the following inventions.

[1] A color-curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains a copper chloride indigo pigment and a yellow dye, and the content of the yellow dye is relative to the coloring pigment. The total amount is 1% by mass or more and 65% by mass or less.

[2] The colored curable resin composition according to Item 1, wherein the copper chloride indigo pigment is a pigment comprising a compound represented by the formula (P1): In the formula (P1), a1, a2, a3, and a4 represent an integer of 0 to 4 independently of each other, and (a1+a2+a3+a4) is 10 or more and 16 or less. ]

[3] The colored curable resin composition according to [1], wherein the copper chloride indigo pigment is C.I. Pigment Green 7.

[4] The colored curable resin composition according to any one of [1], wherein the yellow dye is a yellow azo dye.

[5] The colored curable resin composition according to [4], wherein the yellow azo dye is a dye comprising a compound represented by the formula (1): In the formula (1), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ⁰ is 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.

R ⁵¹ is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent, which may have a hydrogen atom.

P1 is 1 or 2. When p1 is 2, the plural A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different from each other.

When p1 is 1, R ⁵² is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a hydrogen atom or may have a substituent, and when p1 is 2, R ⁵² is a carbon number of 1 to 35 which may have a substituent. The monovalent saturated hydrocarbon group and the -CH ² - contained in the divalent saturated hydrocarbon group may be replaced by -O-, -S-, -CO- or -NR'-.

R' is a monovalent aliphatic hydrocarbon group representing a hydrogen atom or a carbon number of 1 to 6. ]

[6] The colored curable resin composition according to [4], wherein the yellow azo dye is a dye containing a compound represented by the formula (2): [In the formula (2), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, and are contained in Z ¹ , Z ² and Z ³ - CH ² - may be replaced by -CO- or -O-. R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, and may have a monovalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent. A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent. B ¹ and B ² each independently represent 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. ]

[7] A color filter comprising the colored curable resin composition according to any one of [1] to [6].

[8] A display device comprising the color filter according to [7].

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

The colored curable resin composition of the present invention contains a coloring agent (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D), and the coloring agent (A) contains a copper chloride indigo pigment. (hereinafter sometimes referred to simply as "pigment (P)") and yellow dye (hereinafter sometimes referred to as "yellow dye (Y)").

When the coloring agent (A) containing the yellow dye (Y) and the pigment (P) is used, the brightness of the color filter is improved.

The colored curable resin composition of the present invention preferably contains a solvent (E).

Further, the colored curable resin composition of the present invention may contain at least one selected from the group consisting of a polymerization starting aid (D1) and a surfactant (F), if necessary.

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The colorant (A) contains a pigment (P) and a yellow dye (Y), and may further contain a pigment different from the pigment (P) (hereinafter sometimes referred to as "pigment (A2)").

The pigment (P) is preferably a pigment containing a compound represented by the formula (P1).

[In the formula (P1), a1, a2, a3 and a4 are each represented by an integer of 0 to 4, and (a1+a2+a3+a4) is 10 or more and 16 or less. ]

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 still more 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.

The pigment (P) may, for example, be C.I. Pigment Green 7 or the like.

The pigment (P) may be subjected to rosin treatment, if necessary, to surface treatment using a pigment derivative or the like which is introduced with an acidic group or a basic group, and graft treatment of a polymer compound or the like on the surface of the pigment to atomize sulfuric acid. A micronization treatment such as a method, a cleaning treatment using an organic solvent or water for removing impurities, a removal treatment of an ionic impurity by an ion exchange method, or the like. The pigment (P) is ideal for uniform particle size. The pigment dispersant is contained and subjected to dispersion treatment, and a pigment dispersion in which the pigment is dispersed in a uniform state in the solution can be obtained.

The pigment dispersant may, for example, be a pigment dispersant such as a cationic system, an anionic system, a nonionic system, an amphoteric acid, a polyester system, a polyamine system or a acrylonitrile system. These pigment dispersing agents may be used alone or in combination of two or more kinds. For the pigment dispersant, the trade name is KP (Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (made by Zeneca), EFKA (manufactured by CIBA), Ajisper ( Ajinomoto Fine-Techno Co., Ltd., Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

When the pigment dispersant is used, the amount thereof is preferably from 1% by mass to 100% by mass based on the pigment (P), and more preferably from 5% by mass to 50% by mass. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the pigment (P) is preferably 1% by mass or more and 99% by mass or less based on the total amount of the coloring agent (A), and preferably 35% by mass or more and 99% by mass or less, and more preferably 40% by mass or more and 98% by mass or less. The following is more ideal.

The yellow dye (Y) has a maximum absorption wavelength of preferably 400 nm or more and 480 nm or less, more preferably 400 nm or more and 450 nm or less, and more preferably 410 nm or more and 435 nm or less. The maximum absorption wavelength can be obtained by dissolving the dye in a solvent solution and using an absorption spectrum measured by a spectrophotometer, which will be described later in detail.

For the yellow dye (Y), a color index (published by The Society of Dvers and Colorists) is classified as a dye of a yellow dye, and chemical structures include, for example, an azo dye, a metal stinky dye, Quinoline dyes, acridine dyes, anthraquinone dyes, naphthoquinone imine dyes, nitro dyes, methine dyes, indigo dyes and triphenylmethane dyes.

For the yellow dye (Y), for example, CI Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, only numbers are listed.), 13, 14, 15, 19, 21, 23, 24, 25, 25 : 15, 38, 62, 63, 68, 79, 81, 82, 83, 83: 1, 88, 89, 90, 94, 98, 99, 151, 161, 162; CI 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; CI 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; CI The mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62,65;

Among them, the yellow dye (Y) is particularly preferably a yellow azo dye, and is contained, for example, in JP2009-13112-A, JP2009-13290-A, JP2009-13291-A, JP2009-13292-A, JP2009. Dyes of the compounds described in -13293-A, JP 2009-280691-A, JP 2009-299030-A, JP 2010-1469-A, JP 2010-275531-A, JP 2010-275532-A, JP 2010-275533-A.

In the case of the above yellow azo dye, a dye containing a compound represented by the formula (1) is desirable: In the formula (1), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ⁰ is 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.

R ⁵¹ is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent, which may have a hydrogen atom.

P1 is 1 or 2. When p1 is 2, the plural A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different from each other.

When p1 is 1, R ⁵² is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a hydrogen atom or may have a substituent, and when p1 is 2, R ⁵² is a carbon number of 1 to 35 which may have a substituent. The valence saturated hydrocarbon group, the monovalent saturated hydrocarbon group and the -CH ₂ - contained in the divalent saturated hydrocarbon group may be replaced by -O, -S-, -CO- or -NR'-.

R' is a monovalent aliphatic hydrocarbon group representing a hydrogen atom or a carbon number of 1 to 6. ]

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

[In the formula (2), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, and - Z ¹ , Z ² and Z ³ - CH ₂ - may be replaced by -CO- or -O-.

R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, and may have a monovalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent. The carbon number of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms does not contain the carbon number of the substituent, and the number thereof is preferably 2 to 10, more preferably 2 to 8.

The divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may, for example, be an alkyldiyl group having 1 to 16 carbon atoms, and specifically, a methylene group, an ethyl group, a propane diyl group, a butane diyl group, and a pentylene group. Alkyldiyl, hexanediyl, heptanediyl, octanediyl, decanediyl, dodecanediyl and hexadecanediyl.

The -CH ₂ - contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted 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- is preferable. The ideal group may, for example, be -(CH ₂ ) ₃ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -, -(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O- (CH ₂ ) ₂ - and -CH ₂ -CH(CH ₃ )-.

Z ³ is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain -C(=C)-, and an unsubstituted alkanediyl group having 1 to 8 carbon atoms is preferable, and the carbon number is 4 to 8. An unsubstituted alkanediyl group is preferred. The ideal group may, for example, be -(CH ₂ ) ₂ -, -(CH ₂ ) ₄ - and -CH ₂ -C(=CH ₂ )-.

The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms of 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, and is preferably 6 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.

The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a secondary butyl group or a tertiary butyl group. Methyl butyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentane Base, cyclohexyl, methylcyclohexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl.

The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms may be substituted by an alkoxy group or a carboxyl group having 1 to 8 carbon atoms. The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms in the alkoxy group having 1 to 8 carbon atoms may, for example, be a propoxypropyl group (3-(isopropoxy)propyl group or the like), an alkoxy group. Propyl (3-(2-ethylhexyloxy)propyl, etc.) and the like. The aliphatic hydrocarbon group having 1 to 16 carbon atoms which is substituted by a carboxyl group may, for example, be a 2-(carboxy)ethyl group, a 3-(carboxy)propyl group or a 4-(carboxy)butyl group.

The divalent saturated hydrocarbon group having 1 to 35 carbon atoms of R ⁵² may be any of linear, branched or cyclic, and may be a methylene group, a vinyl group, a propane diyl group or a butane 2 group. , pentanediyl, hexanediyl, heptanediyl, octanediyl, decanediyl, tetradecanediyl, hexadecandiyl, cyclopropanediyl, cyclobutanediyl, Cyclopentanediyl, cyclohexanediyl, cycloheptanediyl, cyclooctanediyl, cyclodecanediyl, cyclotetradecanediyl, cyclohexadecanediyl, adamantanediyl and the like. Among them, a linear or branched shape is preferable.

-CH ₂ - contained in the divalent saturated hydrocarbon group having 1 to 35 carbon atoms may be substituted by -O-, -S-, -CO- or -NR'-. The hydrogen atom contained in the divalent saturated hydrocarbon group having 1 to 35 carbon atoms may be substituted by a halogen atom such as a fluorine atom.

The monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms of R' may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a cyclohexyl group.

The hydrogen atom contained in the fluorenyl group having 2 to 18 carbon atoms of R ⁵¹ , R ⁵³ and R ⁵⁴ may be substituted by an alkoxy group having 1 to 8 carbon atoms. The carbon number of the fluorenyl group having 2 to 18 carbon atoms which may have a substituent is counted by the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the thiol group which may have a substituent include an ethyl fluorenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.).

R ⁵³ and R ⁵⁴ are preferably a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, and a fluorenyl group having 2 to 5 carbon atoms. The ideal group may, for example, be a hydrogen atom, an ethyl group or a propyl group.

The divalent aromatic hydrocarbon group having 6 to 14 carbon atoms of A ⁰ , A ¹ and A ² may, for example, be a phenyl group or a naphthalene diyl group. Among them, a phenyl group is preferable.

The substituent of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms may, for example, be 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 or an amine sulfonate. Sulfhydryl, N-substituted amine sulfonyl and the like.

The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a fluorine atom, a chlorine atom or a bromine atom.

The alkyl group having 1 to 8 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a benzyl group or a hexyl group. An alkyl group having 1 to 4 carbon atoms is preferred, an alkyl group having 1 to 2 carbon atoms is preferred, and a methyl group is particularly preferred.

The alkoxy group having 1 to 8 carbon atoms may, for example, be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a secondary butoxy group or a tertiary butoxide. Alkoxy group having a carbon number of 1 to 4, preferably a carbon number of 1 to benzyloxy, hexyloxy or the like The alkoxy group of 2 is preferred, and the methoxy group is particularly desirable.

N-methylamine sulfonyl, N-methylsulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonate, N-isopropylamine sulfonyl, N-butylamine sulfonyl, N -isobutylamine sulfonyl, N-second butylamine sulfonyl, N-tertiary butylamine sulfonyl, N-benzylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl , N-(1,1-dimethylpropyl)amine sulfonyl, N-(1,2-dimethylpropyl)amine sulfonyl, N-(2,2-dimethylpropyl) Aminesulfonyl, N-(1-methylbutyl)amine sulfonyl, N-(2-methylbutyl)amine sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclobenzylamine sulfonyl, N-hexylamine sulfonyl, N-(1,3-dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl)amine sulfonate Sulfhydryl, N-heptylsulfonyl, N-(1-methylhexyl)amine sulfonyl, N-(1,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl , N-(2-ethylhexyl)amine sulfonyl, N-(1,5-dimethyl)hexylamine sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine N-1 substituted sulfonyl sulfonyl group such as sulfonyl group; N,N-dimethylamine sulfonyl group, N,N-ethylmethylamine sulfonyl group, N,N-diethylamine sulfonyl group, N, N-propylmethamine sulfonyl, N,N-isopropylmethylamine sulfonyl, N,N-tert-butylmethylamine N,N-N,N-N-butylethylaminesulfonyl, N,N-bis(1-methylpropyl)aminesulfonyl, N,N-heptylmethylsulfonyl, etc. 2 substituted amine sulfonyl and the like.

The N-substituted amine sulfonyl group is desirably a carbon number of 1 to 16, more preferably a carbon number of 4 to 16.

B ⁰ , B ¹ and B ² each independently represent 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.

The monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms may, for example, be a phenyl group or a naphthyl group.

The monovalent heterocyclic group having 3 to 14 carbon atoms is represented by the following base.

[R, represents a hydrogen atom or an organic group. ]

The organic group may, for example, be the same group as R ⁵⁹ described later.

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 may be a hydroxyl group, an oxo group (oxo), and a monovalent number of carbon atoms of 1 to 16. Substituted by an aliphatic hydrocarbon group, a cyano group, an amine group or an N-substituted amine group.

As the N-substituted amine group, it is preferred to use a -NHR ⁵⁷ group and a -NR ⁵⁷ R ⁵⁸ group. However, R ⁵⁷ and R ⁵⁸ each independently represent a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent. The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms are the same as those described above.

It is preferable that B ¹ and B ² are the same kind of base, and further, A ¹ and A ² , R ⁵³ and R ⁵⁴ , and Z ¹ and Z ² are each a group of the same kind. When these are the bases, the compound represented by the formula (2) is easily produced.

B ⁰ , B ¹ and B ² are each independently a group represented by the formula (2-a).

[In the formula (2-a), R ⁵⁹ is a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which represents a hydrogen atom or 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 formula (2) indicate that the compound contains a group represented by the formula (2-a), these also contain tautomers.

The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms is the same as the above. R ^{59 is} preferably methylbutyl (1,1,3,3-tetramethylbutyl, etc.), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl) And a branched aliphatic hydrocarbon group such as methylcyclohexyl (2-methylcyclohexyl) or the like, alkoxypropyl (3-(2-ethylhexyloxy)propyl or the like).

The substituent of R ⁵⁹ and R ⁶⁰ may, for example, be a hydroxyl group, a halogen atom, an alkoxy group having 1 to 8 carbon atoms or a decyloxy group having 1 to 8 carbon atoms. The alkoxy group having 1 to 8 carbon atoms is the same as the above. The methoxy group having 1 to 8 carbon atoms is an ethoxycarbonyl group, a propenyloxy group, a hexylcarbonyloxy group, a octylcarbonyloxy group, a benzhydryloxy group or the like.

R ⁶⁰ is preferably a methyl group.

The compound represented by the formula (1) is a compound described in JP2010-275531-A, and a compound represented by the formula (1-1) to the formula (1 to 10) is preferred. In the table, A ¹ , A ² , Z ¹ and Z ² , the bond on the right represents a bond closer to Z ³ .

The compound represented by the formula (2) can be produced by the method described in JP2010-275531-A.

The content of the yellow dye (Y) is preferably 1% by mass or more and 15% by mass or less based on the total amount of the coloring agent (A), and preferably 2% by mass or more and 55% by mass or less.

The coloring agent (A) may further contain a pigment (A2) together with the pigment (P) and the yellow dye (Y).

The aforementioned pigments may be exemplified by a color index (published by The Society of Dyes and Colourists) as a pigment. Among them, yellow pigments and green pigments are particularly desirable.

For the yellow pigment, for example, CI Pigment Yellow 1,3,12,13,14,15,16,17,20,24,34,53,83,86,93,94,109,110,117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., and the yellow pigments disclosed in JP2001-354869-A, JP 2007-224176-A, and the like.

As the green pigment, C.I. Pigment Green 36, 58 and the like can be mentioned.

Among these, as pigment (A), C.I. Pigment Yellow 138, 139, 150; C.I. Pigment green 36, 58 is ideal. Since these pigments are contained, the transmission spectrum is easily optimized, and the chemical resistance is improved. These pigments may be used alone or in combination of two or more.

The pigment (A2) may be subjected to a rosin treatment, a surface treatment such as a pigment derivative introduced with an acidic group or a basic group, a graft treatment of a polymer compound or the like on the surface of the pigment, or a fine particle of sulfuric acid. The micronization treatment or the cleaning treatment using an organic solvent or water for removing impurities, and the ionic impurities are detoxified by an ion exchange method or the like.

Pigment (A2), uniform particle size is ideal. By dispersing the pigment dispersant, it is possible to obtain a pigment dispersion in a state in which the pigment is uniformly dispersed in the solution. It is also possible to mix the pigment (P) and the pigment (A2) and perform dispersion treatment together.

Examples of the pigment dispersant include a cationic dispersant such as a cationic system, an anionic system, a nonionic system, an amphoteric acid, a polyester system, a polyamine system, and an acrylic resin. These pigment dispersing agents may be used alone or in combination of two or more kinds. The product name is KP (Shin-Etsu Chemical Co., Ltd.), Flowlen (Kyoei Chemical Co., Ltd.), Solsperse (Zeneca), EFKA (made by CIBA), Ajisper (Ajinomoto) -Techno (share) system, Disperbyk (manufactured by BYK-Chemie Co., Ltd.), etc.

When the pigment dispersant is used, the amount of the pigment (A2) 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. When the amount of the pigment dispersant used is within the above range, there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

When the pigment (A2) is contained, the content ratio is preferably from 1% by mass to 90% by mass in the coloring agent (A), and preferably from 3% by mass to 80% by mass. When this ratio is made, the transmission spectrum is easily optimized, and the resulting color filter has a contrast ratio. Brightness, heat resistance, and chemical resistance tend to be excellent.

When the colorant (A) contains the pigment (P) and the yellow dye (Y), the content of the colorant (A) is the same as the total amount of the colorant (A), and the pigment (P); 35 mass% or more and 99 mass% or less The yellow dye (Y); preferably 1% by mass or more and 65% by mass or less, preferably the pigment (P); 40% by mass or more and 98% by mass or less of the yellow dye (Y); and 2% by mass or more and 55% by mass or less.

When the colorant (A) contains the pigment (A2), the content of the pigment (P), the yellow dye (Y), and the pigment (A2) is the total amount of the colorant (A), and the pigment (P); % or more of 98% by mass or less of yellow dye (Y); 1% by mass or more and 66% by mass or less of pigment (A2); 1% by mass or more and 90% by mass or less, preferably pigment (P); 9% by mass or more and 97% by mass or less of yellow Dye (Y); 2% by mass or more and 55% by mass or less of the pigment (A2); preferably 1% by mass or more and 85% by mass or less.

The content of the colorant (A) is preferably from 5% by mass to 70% by mass, more preferably from 8% by mass to 60% by mass, even more preferably from 10% by mass to 57% by mass on the solid content in the colored curable resin composition. quality%. Here, the solid content means the total of the components of the solvent in addition to the coloring curable resin composition. When the content of the colorant (A) is within the above range, a desired color can be obtained when a color filter is used. The light and the color concentration can be made to contain a necessary amount of the resin and the polymerizable compound in the composition, so that a pattern having sufficient mechanical strength can be formed.

<Resin (B)>

The resin (B) is not particularly limited, but an alkali-soluble resin is preferred.

Examples of the resin (B) include the following resins [K1] to [K6].

The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)"), and a ring having 2 to 4 carbon atoms. a copolymer of an ether structure and an ethylenically unsaturated bond (b) (hereinafter sometimes referred to as "(b)"); a resin [K2] (a) and (b), and (a) copolymerizable Monomer (c) (however, different from (a) and (b).) (hereinafter sometimes referred to as "(c)") copolymer; copolymer [K3] (a) and (c) copolymer Resin [K4] copolymer of (a) and (c) and (b) resin; resin [K5] (b) and (c) copolymer and (a) resin; resin [K6] ( b) a resin which reacts with the copolymer of (c) with (a) and then with a carboxylic anhydride.

(a), specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinyl benzoic acid; maleic acid, fumaric acid, Methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl decanoic acid, 4-vinyl decanoic acid, 3,4,5,6-tetrahydrofurfuric acid, 1,2,3,6 - an unsaturated dicarboxylic acid such as tetrahydrofurfuric acid, dimethyltetrahydrofurfuric acid or 1,4-cyclohexenyl dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid , 5-carboxybicyclo[2.2.1] Hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5- Ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]heptane- a carboxyl group-containing bicyclic unsaturated compound such as 2-alkenyl; maleic anhydride, methyl maleic anhydride, methyl fumaric anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dicarboxylic acid such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride Unsaturated polyvalent carboxylic acid such as acid anhydride; succinic acid mono [2-(methyl) propylene methoxyethyl ester], decanoic acid mono [2-(methyl) propylene methoxyethyl ester] A mono[2-(methyl)propenyloxyalkyl]ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid and maleic anhydride are preferred from the point of copolymerization reactivity and solubility in an aqueous alkali solution.

In the present specification, "(meth)acryl fluorenyl group" means at least one selected from the group consisting of an acryloyl group and a methacryl fluorenyl group. The expressions "(meth)acrylic acid" and "(meth) acrylate" have the same meaning.

(b) is, for example, at least one selected from the group consisting of a cyclic ether structure having a carbon number of 2 to 4 (for example, an oxirane ring, an oxetane ring, and a tetrahydrofuran ring). a polymerizable compound with an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a methacryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. "(Meth)acrylonitrile" and "(A The expression "base" acrylate" has the same meaning.

(b), for example, a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes abbreviated as "(b1)"), and having an oxypropylene group ( Oxetanyl) a monomer (b2) having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes abbreviated as "( B3)") and so on.

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes abbreviated as "(b1-1)")) A monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(b1-1), for example, glycidyl methacrylate, β-methylglycidyl methacrylate, β-ethylglycidyl methacrylate, and epoxypropyl vinyl ether , o-vinylbenzyl epoxypropyl ether, m-vinylbenzyl epoxypropyl ether, p-vinylbenzyl epoxypropyl ether, α-methyl-o-vinylbenzyl epoxypropyl ether, α-Methyl-m-vinylbenzyl epoxypropyl ether, α-methyl-p-vinylbenzyl epoxypropyl ether, 2,3-bis(glycidoxymethyl)styrene, 2 , 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(epoxypropoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxy) Methyl)styrene, 3,4,5-tris(epoxypropoxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

(b1-2), for example, vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 (Daicel Chemical Industry Co., Ltd.), A 3,4-Epoxycyclohexyl acrylate (for example, Cyclomer (manufactured by Daicel Chemical Industry Co., Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II).

[In the formulae (I) and (II), Rb ¹ and Rb ² represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - RS- or * -R ^b3 -NH-. R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. * indicates the bond with O. ]

The alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a secondary butyl group or a tertiary butyl group.

The alkyl group in which the hydrogen atom is replaced by a hydroxyl group may, for example, be a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group or a 3-hydroxypropyl group. Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and the like.

R ^b1 and R ^{b2 are} desirably a hydrogen atom, a methyl group, a methylol group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, preferably a hydrogen atom or a methyl group.

The alkanediyl group may, for example, be a methylene group, an ethyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane-1,5 group. - Diyl, hexane-1,6-diyl and the like.

X ^b1 and X ^b2 , ideally a single bond, methylene, ethyl, *-CH ₂ -O-, or *-CH ₂ CH ₂ -O-, more preferably a single bond or *-CH ₂ CH ₂ -O-(* table and O bond).

The compound represented by the formula (I) may be any of the compounds represented by the formula (I-1) to the formula (I-15). Wherein, in particular, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), and the formula (I-11) to the formula (I) -15) Any compound expressed is ideal, (I-1), a compound represented by the formula (I-7), the formula (I-9) or the formula (I-15) is preferred.

The compound represented by the formula (II) may be any of the compounds represented by the formula (II-1) to the formula (II-15). Wherein, in particular, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), and the formula (I-11) to the formula (II) Any compound represented by -15) is desirable, and a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15) is preferred.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or in combination at any ratio. When used in combination, 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 90:10, more preferably 20:80 To 80:20.

In the case of the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxypropylene group and a methacryloxy group is preferable. (b2), 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-methylpropenyl oxymethyl propylene oxide, 3-ethyl-3 -Methyl propylene oxime methyl propylene oxide, 3-ethyl-3-methyl propylene oxime oxymethyl propylene oxide, 3-methyl-3-methyl propylene oxiranoxy propylene oxide, 3- Methyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-methyl propylene oxirane ethyl epoxide Propane, etc.

In the case of the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuranyl group and a methacryloxy group is preferable.

(b3) Specifically, tetrahydrofuran acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Co., Ltd.) and tetrahydrofuran methacrylate are used.

In the point that the heat resistance and chemical resistance of the obtained color filter can be improved, (b) is preferable to (b1), and the storage stability of the colored curable resin composition is excellent. , (b1-2) is ideal.

(c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this In the technical field, the conventional name is "dicyclopentanyl (meth)acrylate". Also, it is sometimes called "tricyclodecyl (meth)acrylate".), tricyclo(meth)acrylate [5.2.1.0 ^{2 , 6} ]nonene-8-yl ester (known in the art as "dicyclopentyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, (methyl) ) isobornyl acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (Meth) acrylates such as benzyl (meth) acrylate; 2-hydroxy methacrylate An ester of a hydroxyl group-containing methacrylic acid such as an ester or a 2-hydroxypropyl methacrylate; a dicarboxylic acid diester such as diethyl maleate, dipropyl fumarate or 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(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 - tertiary butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]heptane- 2-ene, 5,6-bis(tertiary butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1 a bicyclic unsaturated compound such as hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, 3-malaya N-ammonium imino ester of amine benzoate, N-succinimide ester of 4-maleimide butyrate, N-succinimide ester of 6-maleimide hexanoate, 3- N-ammonium imino ester of melamine propionate, dicarbonyl quinone imine derivatives such as N-(9-acridinyl)maleimide; styrene, α-methylstyrene , m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacryl Amine, ethylene acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, especially from the point of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmalazone Amines are ideal.

In the resin [K1], the ratio of the structural units derived from the respective constituents constitutes the entire structural unit of the resin [K1], (a) the structural unit of the source; the structural unit of the source of 2 to 60 mol% (b); 98% Mo is % ideal, (a) source of structural units; 10 to 50 mole % (b) source of structural units; 50 to 90 mole % is preferred.

When the ratio of the structural unit of the resin [K1] is in this range, the coloring curable resin composition retains stability, developability in forming a colored pattern, and the solvent resistance of the obtained colored pattern tends to be excellent.

Resin [K1], for example, can be referred to the method described in the "Experimental Method for Polymer Synthesis" (Otsuka Ryokan, Ltd., 1st Edition, 1st Edition, 1st March, 1972). Manufactured from the literature cited in the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, and for example, nitrogen is substituted for oxygen to cause a deoxidation ring. Environment, heating, and heat preservation method under stirring. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and a compound which is generally used in the art can be used. For example, the polymerization initiator may be an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic The peroxide (such as benzamidine peroxide) may be a solvent (E) or the like which will be described later as a solvent for coloring the curable resin composition.

In this case, the obtained copolymer may be used as it is and may be used as it is. The concentrated or diluted solution may be used as a solid (powder) by reprecipitation or the like, and may be taken out and used. In particular, in the case of this polymerization, it is used as a solvent, and by using the solvent (E) described later, 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 respective source building blocks, constitutes the entire structural unit of the resin [K2], (a) the source of the structural unit; 2 to 45 mol% (b) of the source of the structural unit; 95 mole % (c) source of structural unit; 1 to 65 mole % is ideal, (a) source of structural units; 5 to 40 mole % (b) source of structural units; 6 to 80 mole % ( c) The source of the structural unit; 5 to 60 mol% is preferred.

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 in forming a colored pattern, and the solvent resistance, heat resistance and mechanical properties of the obtained colored pattern Excellent strength tendency.

The resin [K2] is produced, for example, in the same manner as described in the method for producing the resin [K1].

In the resin [K3], the ratio of the structural units of the respective sources constitutes the entire structural unit of the resin [K3], (a) the structural unit of the source; the structural unit of the source of 2 to 60 mol% (c); Up to 98% is ideal.

(a) The source of the structural unit; 10 to 50 mole % (c) of the source of the structural unit; 50 to 90 mole % is preferred.

The resin [K3] is produced, for example, in the same manner as described in the method for producing the resin [K1].

Resin [K4], after obtaining a copolymer of (a) and (c), (b) all of the cyclic ethers having 2 to 4 carbon atoms may be added to (a) all of the carboxylic acids and/or carboxylic anhydrides. Manufacturing.

First, the copolymer of (a) and (c) was produced in the same manner as described in the method for producing the resin [K1]. At this time, the ratio of the structural unit derived from each other is preferably the same as the ratio given in the resin [K3].

Next, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the copolymer is reacted with (b) all cyclic ethers having 2 to 4 carbon atoms.

After the manufacture of the copolymers of (a) and (c), the gas in the flask is replaced by nitrogen to air, (b) the reaction catalyst of a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris(dimethyl) The amine methyl phenol or the like and a polymerization inhibitor (for example, hydroquinone) are placed in a flask, for example, at 60 to 130 ° C for 1 to 10 hours to produce a resin [K4].

The amount of (b) used is ideal for (a) 100 moles, 5 to 80 moles, and more preferably 10 to 75 moles. In this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern tend to be good. The cyclic ether has high reactivity, and the unreacted (b) does not easily remain. Therefore, (b) for the resin [K4] is preferably (b1), and (b1-1) is preferred.

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibiting agent used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the charging method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment and the calorific value of the polymerization. Here, similarly to the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment and the calorific value of the polymerization.

In the first step, the resin [K5] obtained the copolymer of (b) and (c) in the same manner as the above-mentioned method for producing the resin [K1]. Similarly to the above, the obtained copolymer may be used as it is without being subjected to the reaction, or may be obtained by taking out a solid (powder) by a method such as concentration or dilution, reprecipitation or the like.

The ratio of the structural unit derived from (b) and (c) is the total number of moles of the total structural unit of the above copolymer, and is preferably in the following range.

(b) source of structural units; 5 to 95 mole % (c) source of structural units; 5 to 95 mole % ideal, (b) source of structural units; 10 to 90 moles of (c) source Construction unit; 10 to 90% by mole More ideal.

Further, under the same conditions as in the method for producing the resin [K4], all of the copolymers derived from (b) and (c) have a cyclic ether derived from (b), and (a) all carboxylic acids or carboxylic anhydrides. The reaction is carried out to obtain a resin [K5].

The amount of (a) used in the reaction with the aforementioned copolymer is preferably (b) 100 mol, and 5 to 80 mol. The cyclic ether has high reactivity, and the unreacted (b) does not easily remain. Therefore, (b) which is used together with the resin [K5] is preferably (b1), and further preferably (b1-1).

The resin [K6] is a resin which reacts the resin [K5] with a carboxylic acid anhydride.

The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride is reacted with a carboxylic acid anhydride.

The carboxylic anhydride may, for example, be 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 (himic anhydride) and the like. The amount of the carboxylic anhydride to be used is preferably from 0.5 to 1 mol per mol of the (a).

Specific examples of the resin (B) include a (meth) acrylate 3,4-epoxycyclohexylmethyl ester/(meth)acrylic acid copolymer, and an acrylic 3,4-epoxytricyclo[5.2. 1.0 ^2.6 ] Resin of oxime ester/(meth)acrylic acid copolymer [K1]; (meth)acrylic acid propyl acrylate / (meth) acrylate / (meth) acrylate copolymer, (methyl) Glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo(5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide Copolymer, 3,4-epoxytricyclo[?.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/vinyltoluene/dicyclopentenyl (meth)acrylate copolymer, 3-methyl- Resin of 3-(meth)acryloyloxymethyl propylene oxide/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene /(Meth)acrylic acid copolymer resin [K3]; (meth)acrylic acid benzyl ester / (meth)acrylic acid copolymer addition (meth)acrylic acid propyl acrylate resin, (meth)acrylic acid Cyclodecyl ester/styrene/(meth)acrylic acid copolymer addition of glycidyl (meth)acrylate Resin, resin such as trimethyl decyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate copolymer (meth) acrylate (meth) acrylate [K4]; Copolymer of tricyclodecyl acrylate/glycidyl (meth) acrylate with (meth)acrylic acid, tricyclodecyl (meth) acrylate/styrene/(meth) acrylate epoxy a copolymer of a copolymer of propyl ester and a resin reactive with (meth)acrylic acid [K5]; a copolymer of tricyclodecyl (meth)acrylate/epoxypropyl (meth)acrylate and (meth)acrylic acid The resin [K6] or the like of a resin such as a resin which is reacted with tetrahydrophthalic anhydride.

Among them, as the resin (B), it is preferable that the resin [K1], the tree finger [K2], and the resin [K3] are preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is desirably 3,000 to 10,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is increased, and the residual film ratio is also high, and 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 desirably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) is desirably 50 to 170 mg-KOH/g, more desirably 60 to 160 mg-KOH/g, more desirably 70 to 135 mg-KOH/g. The acid value here is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

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

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by active radicals and/or acids generated by the polymerization initiator (D) by light or heat, and examples thereof include polymerizable ethylenic unsaturation. A compound of a bond or the like is preferably a methacrylate compound.

The polymerizable compound (c) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and hexa(meth)acrylic acid. Dipentaerythritol ester, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol penta(meth)acrylate, tris(2-(A) Base) propylene oxiranyl ethyl) iso-cyanate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified tetra (A) Pentaerythritol acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, and the like. Among them, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferred.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the solid content of the colored curable resin composition. When the content of the polymerizable compound (C) is within the above range, the curing proceeds sufficiently, and the film thickness ratio before and after the development is increased. The pattern is prone to undercut and the adhesion is good, so it is ideal.

<Polymerization initiator (D)>

The polymerization initiator (D) is a compound which can generate a living radical, an acid or the like by light or heat, and the polymerization can be started, and a known polymerization initiator can be used.

The polymerization initiator (D) may, for example, be an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound or a biimidazole compound.

The O-indenyl ruthenium compound is a partially structured compound represented by the formula (d1).

Hereinafter, * indicates a bond.

For the O-indenyl hydrazine compound, for example, N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy- 1-(4-Phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentane-1 -keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1- Imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2-4-dioxolylmethyloxy) Benzomeptyl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydrazide -9H-carbazol-3-yl]-3-cyclopentylpropan-1-amine, N-benzylidene-1-(9-ethyl-6-(2-methylphenyl) Indenyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Use Irgacure (registered trademark) Products such as OXE 01, OXE 02 (above, manufactured by BASF Corporation), N-1919 (made by Adeka Co., Ltd.), and the like 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 configurations may have a substituent.

The compound having a partial structure represented by the formula (d2) may, for example, be 2-methyl-2-(N-morpholinyl)-1-(4-methylthiophenyl)propan-1-one. ,2-dimethylamino-1-(4-N-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4- Methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Products such as Irgacure (registered trademark) 369, 907 and 379 (above, manufactured by BASF Corporation) may be used.

The compound having a partial structure represented by the formula (d3) may, for example, be 2-hydroxy-2-methyl-1-phenylpropan-1-one or 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- A low polymer of a ketone, α,α-diethoxyethyl benzene, benzyl dimethyl ketal, and the like.

At the point of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis (three) Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-three Pyrazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(5-methylfuran) 喃-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3 ,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamine-2-methylphenyl)vinyl]-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

The mercaptophosphine compound may, for example, be a 2,4,6-trimethylbenzimidyldiphenylphosphine oxide compound. A product such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) may be used.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3) may be mentioned. -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JP6-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2- Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxy) Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis (2 -Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPH62-174204-A, etc.), 4, 4' An imidazole compound in which a phenyl group at the 5,5'-position is substituted with a carbonyl alkoxy group (for example, refer to JPH07-10913) and the like.

Further, for the polymerization initiator (D), benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone, O-benzonitrile Methyl benzoate, 4-phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra (tertiary-butyl a diphenyl ketone compound such as dicarbonyl ketone or 2,4,6-trimethyldiphenyl ketone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone or the like ; 10-butyl-2-chloroacridone, benzil, methyl glyoxylate, titanocene compound, and the like. These are, in contrast to the polymerization initiator (D1) described later (special It is an amine) combination is ideal.

The acid generator may, for example, be 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate or 4-ethyloxyphenylphenyl Methyl hydrazine p-toluene sulfonate, 4-ethyl methoxy phenyl. methyl. Benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate Such as sulfonium salts, and nitrated benzyl tosylate, benzoin tosylate and the like.

The polymerization initiator (D) contains at least one selected from the group consisting of an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, and a biimidazole compound. The polymerization initiator is preferably a polymerization initiator containing an O-fluorenyl ruthenium compound, and a polymerization initiator containing an O-fluorenyl ruthenium compound and an alkylphenone compound is more preferable.

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

A polymerization starting aid (D1) may be further contained together with the polymerization initiator (D). The polymerization initiation aid (D1) is a compound for promoting polymerization of a photopolymerizable compound which initiates polymerization by a polymerization initiator, or is a sensitizer.

The polymerization starting aid (D1) may, for example, be an amine compound, an alkoxy fluorene compound, a Thioxanthone compound, a carboxylic acid compound or the like.

The amine compound may, for example, be triethanolamine, methyl glycolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-di Methylammonium isoamyl benzoate, 2-dimethylaminoethyl benzoate, 4-dimethyl 2-Ethyl hexyl benzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenyl ketone (commonly known as Michler's ketone) , 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethylmethylamino)diphenyl ketone, etc., especially 4,4'-double ( Diethylamino)diphenyl ketone is desirable. It is also possible to use a product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxy ruthenium compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylethylphenylthioacetic acid, and methoxybenzene. Thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine Acid, naphthyloxyacetic acid, and the like.

As the polymerization starting aid (D1), a thioxanthone compound is desirable.

In addition, when the polymerization initiator (D1) is used, the amount of the resin (B) and the polymerizable compound (C) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Parts by mass. Further, the content of the polymerization initiator (D) is preferably from 20 to 100 parts by mass, more preferably from 30 to 80 parts by mass, per 100 parts by mass. When the amount of the polymerization initiator (D1) is in this range, it is possible to form a pattern with high sensitivity, and there is a tendency for a color filter having a higher brightness.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is generally used in the art can be used. For example, an ester solvent (a solvent containing -COO-), an ether solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-), a ketone solvent other than the ester solvent (solvent containing -CO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine or the like is selected and used.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and acetic acid. Amyl ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, acetic acid ring Hexyl ester, γ-butyrolactone, and the like.

The ether solvent may, for example, be ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, or Ethylene 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-butyl Alcohol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, phenyl methyl ether, phenyl ethyl ether, methyl phenyl methyl ether and the like.

The ether ester solvent may, for example, be methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate or 3-methoxypropene. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropane Ethyl acetate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, 2 Ethyl ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether ester, acetic acid Glycol monoethyl ether ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 4-methyl-2. - Pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

The alcohol solvent may, for example, be methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol or glycerin.

The aromatic hydrocarbon solvent may, for example, be benzene, toluene, xylene or mestililene.

The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of from 1 to 10 (101.326 kPa) of from 120 ° C to 180 ° C is preferred from the viewpoint of coatability and dryness. Among them, especially propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, two Ethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethyl Preferred is guanamine, etc., propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butyl Alcohol and ethyl 3-ethoxypropionate are preferred.

The content of the solvent (E) in the coloring curable resin composition is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the coloring curable resin composition. In other words, the colored hardenable tree refers to the solid component of the composition, ideally 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 is not insufficient, and the display characteristics tend to be improved.

<Interacting Agent (F)>

The surfactant (F) may, for example, be a decane-based surfactant, a fluorine-based surfactant, a fluoroantane-based surfactant having a fluorine atom or the like. These may also have a polymeric group on the branch.

The surfactant of the above-mentioned oxane-based surfactant may, for example, be a surfactant of a decane bond. Specifically, Toray oxirane DC3PA, same as SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (Toray. Dow Corning), KP321, KP 322, KP323, KP 324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materails, manufactured by Japan Contract Corporation) and the like.

The fluorine-based surfactant may, for example, be a fluorocarbon chain surfactant or the like. Specifically, Fluorad (trade name) FC430, FC431 (Sumitomo 3M (share) system), Megafac (registered trademark) F142 D, F171, F172, F173, F177, F183, and R30, Same as RS-718-K (DIC system), Eftop (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi Material Electronic Co., Ltd.), Surflon (registered trademark) S381, same as S382, The same as SC101, the same as SC105 (made by Asahi Glass Co., Ltd.), E5844 (made by Daikin Fine Chemicals Research Institute), and the like.

The fluorine atom-containing siloxane-based surfactant may, for example, be a surfactant of a siloxane chain or a fluorocarbon chain. Specifically, Megafac (login Standard) R08, same as BL20, with F475, with F477, with F443 (DIC).

The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05% by mass or less, based on the coloring curable resin composition. the following. However, the content of the above-mentioned surfactant (F) does not contain the content of the above-mentioned pigment dispersant. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain a filler, other polymer compound, adhesion promoter, oxidation inhibitor, ultraviolet absorber, light stabilizer, chain shifting agent, etc., if necessary. Kind of additive.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and a polymerization initiator which is used if necessary (D1), the solvent (E), the surfactant (F) and other components are mixed and prepared.

The pigment (P) is preferably mixed with the solvent (E) in advance, and the average particle diameter of the pigment is about 0.2 μm or less, and is dispersed by using a bead mill or the like. In this case, the pigment dispersant or a part or all of the resin (B) may be blended as necessary. In the obtained pigment dispersion, the yellow dye (Y), the balance of the resin (B), and the polymerizable compound (C), and, if necessary, the polymerization initiator (D), the solvent (E) The remaining amount of the surfactant (F) and other components are mixed to a predetermined concentration, and the intended color-curable resin composition can be prepared.

The yellow dye (Y) can also be dissolved in the solvent (E) to prepare a solution. The The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

The colored curable resin composition prepared by the above mixing is preferably filtered by a filter having a pore diameter 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 green color filter. With a blue green color filter, for example, a C light source, the CIE chromaticity coordinates in a 2 degree field of view are ideally in the range of 0.140 ≦ x ≦ 0.270, 0.500 ≦ y ≦ 0.690, preferably 0.170 ≦ x ≦ 0.260, 0.500. The range of ≦y ≦ 0.680, more preferably in the range of 0.200 ≦ x ≦ 0.250, 0.560 ≦ y ≦ 0.680, can obtain a brilliant blue-colored green color filter.

The method of producing the colored pattern of the color filter from the colored curable resin composition of the present invention may be a photolithography method, an inkjet printing method, a printing method, or the like. Among them, photolithography is ideal. The photolithography method is a method in which the colored curable resin composition is applied onto a substrate, dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film of a cured product of the above composition layer can be formed without exposure to a photomask and/or without development.

The film thickness of the color filter to be produced is not particularly limited, and may be appropriately adjusted depending on the purpose and use, for example, 0.1 to 30 μm, desirably 1 to 20 μm, and more desirably 1 to 6 μm.

For the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda-lime glass covered with cerium oxide, and polycarbonate, polymethyl acrylate, and poly-pair can be used. A resin plate such as ethylene phthalate or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Also on these substrates Other color filter layers, resin layers, transistors, circuits, and the like can be formed.

Photolithography forms various color pixels and can be carried out using well-known or conventional devices and conditions. For example, it can be produced by the method described below.

First, the colored curable resin composition is applied onto a substrate, dried by heating (pre-baked), and/or dried under reduced pressure to remove volatile components such as a solvent, and dried to obtain a smooth composition layer.

The coating method may, for example, be a spin coating method, a slit coating method, a slit spin coating method, or the like.

The temperature at which heat drying is carried out is preferably 30 to 120 ° C, and preferably 50 to 110 ° C. In terms of heating time, 10 seconds to 60 minutes is ideal, and 30 seconds to 30 minutes is preferable.

When the vacuum drying is carried out, a temperature range of 20 to 25 ° C is preferably carried out at a pressure of 50 to 150 Pa.

The film thickness of the composition layer is not particularly limited, and can be appropriately adjusted depending on the thickness of the color filter for the purpose.

Next, the composition layer is exposed through a mask that forms a colored pattern of the desired color. The pattern on the reticle is not particularly limited, and a graphic suitable for the purpose is used.

For a light source for exposure, a light source that produces light having a wavelength of 250 to 450 nm is desirable. For example, light of less than 350 nm is divided by a filter that divides this wavelength range, and light near 436 nm, around 408 nm, and around 365 nm is selected by using a band bass filter that takes out these wavelength domains. It can also be taken out.

Specifically, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, or the like can be given.

In order to uniformly illuminate the parallel light on the exposed surface, or to accurately align the reticle with the substrate, it is desirable to use an exposure device such as a reticle aligner and a stepper.

The exposed composition layer is brought into contact with the developer to develop, and a colored pattern is formed on the substrate. Through development, the unexposed portion of the composition layer is dissolved in the developer to be removed.

The developer may, for example, be preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide. The concentration in the aqueous solution of these basic compounds is desirably 0.01 to 10% by mass, preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The developing method may be any one of a paddle method, a dipping method, and a spray method. Further, the substrate can be tilted at an arbitrary angle during development.

It is ideal to wash with water after development.

Furthermore, it is desirable to bake the obtained colored graphics after the implementation. After baking temperature, 150 to 250 ° C is ideal, 160 to 285 ° C is ideal. After baking time, 1 to 120 minutes is ideal, and 10 to 60 minutes is ideal.

The colored pattern and the colored coating film thus obtained are used as a color filter.

According to the colored curable resin composition of the present invention, a blue color green color filter having a particularly high brightness can be produced, and the color filter is used in a display device (for example, a liquid crystal display device, an organic EL device, etc.). It is used as a color filter in electronic paper, solid-state imaging element, etc.

Example

Next, the present invention will be more specifically described by way of examples. The "%" and "parts" in the examples are, if not specified, the mass % and mass parts.

Synthesis Example 1

After adding 200 parts of water to 10 parts of m-toluidine-4-sulfonic acid (the compound represented by the formula (a-2)), it was adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling.

The following operations were carried out under ice cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. 39 parts of 35% hydrochloric acid was added in small portions to form a brown solution, followed by stirring for 2 hours. An aqueous solution in which 10.1 parts of thioguanamine was dissolved in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

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

The following operations were carried out under ice cooling. After stirring the aqueous solution of pyrrolidone to a colorless solution, the mixture was adjusted to pH 8 to 9 with a 30% aqueous sodium hydroxide solution, and the suspension containing the diazonium salt was dripped for 2 hours. After the completion of the dropwise addition, stirring was further carried out for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 21.4 parts (yield: 87%) of the compound of the formula (d-3).

Compound (d-3) 0.35g was dissolved in N, N- dimethylformamide become the volume 250cm ^3, in which the 2cm ³ was diluted with water to a volume of 100cm ³ (concentration: 0.028g / 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 λ max = 433 nm.

In a flask equipped with a cooling tube and a stirring device, 5.0 parts of the compound (d-3), 35 parts of acetonitrile and 1.6 parts of N,N-dimethylformamide were added, and the mixture was kept at 20 ° C or lower under stirring, and thidium was added dropwise thereto. 2.4 parts of chlorine. After the completion of the dropwise addition, the temperature was raised to 40 ° C, and the reaction was maintained at the same temperature for 2 hours, followed by cooling to 20 ° C. The cooled reaction solution was poured into 150 parts of ice water with stirring, and stirred for 30 minutes. The precipitated yellow crystals were filtered, washed thoroughly with tap water, and dried under reduced pressure at 60 ° C for 2 hours. In addition, a flask equipped with a cooling tube and a stirring device was prepared, and 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were added, and the mixture was maintained at 20 ° C or lower under stirring, and the previously prepared yellow crystal was allowed to stand for 1 hour. Join. After the yellow crystals were added, the temperature of the solution was raised to room temperature, and the reaction solution was stirred for 30 minutes. After adding 40 parts of methanol to the reaction solution and stirring, the mixed solution was added to a mixed liquid of 29 parts of acetic acid and 300 parts of ion-exchanged water under stirring to precipitate crystals. The precipitated crystals were filtered, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 8.9 parts of a compound represented by formula (III-3) (yield 69%).

Compound (III-3) 0.35g was dissolved in ethyl lactate to become the volume 250cm ^3, in which the 2cm ³ diluted with ion-exchanged water so that the volume becomes 100cm ³ (concentration: 0.028g / l), with a spectrophotometer (Quartz cell, optical path length; 1 cm) The absorption spectrum was measured. This compound showed an absorbance of 2.3 (arbitrary unit) at λ max = 431 nm.

The following reaction was carried out under nitrogen. After 150 parts of N-methylpyrrolidone was added to 49.9 parts of the compound (III-3), the mixture was stirred for 30 minutes to prepare a reaction solution. At room temperature, the reaction solution was stirred, and 6.8 parts of ruthenium dichloride was dropped. After the end of the drip, stir for another 8 hours. 7.8 parts of diclofenac was added dropwise. After the end of the drip, stir for another 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added and stirred for 30 minutes.

The organic phase was separated by a separatory funnel, and then washed with 500 parts of water, 3000 parts of a 10% sodium carbonate aqueous solution, 1000 parts of a 10% aqueous acetic acid solution, and 1000 parts of ion-exchanged water.

The solvent of the fractionated organic phase was distilled off to obtain 2.0 parts of a dye (a) of a mixture of the compound represented by the formula (1-6) and the compound represented by the formula (1-7). The yield was 85%.

0.35 g of the dye (a) was dissolved in ethyl lactate to have a volume of 250 cm ³ , and 2 cm ^{3 of} the dye (a) was diluted with ion-exchanged water to have a volume of 100 cm ³ (concentration: 0.028 g/l), and a spectrophotometer (quartz tank) was used. , optical path length; 1 cm) Determination of absorption spectrum. This compound showed an absorbance of 2.2 (arbitrary unit) at λ max = 431 nm.

<Measurement of content ratio in mixture>

The content ratio of the compound represented by the formula (1-6) in the dye (a) to the compound represented by the formula (1-7) is measured by a high-speed liquid chromatography (HPLC) according to the quantitative method. The calibration curve method is a method for determining the unknown concentration from the concentration-absorbance relationship of a series of standard solutions of known concentration when determining the concentration of the substance in the solution.

HPLC device Prominence (made by Shimadzu Corporation)

Liquid feeding unit: LC-20AT two sets

Autosampler: SIL-20A

Column oven: CTO-20A

UV detector: SPD-20A

Online degasser: DGU-20A

Column Wakosil II 3C18HG (3μm, 3mm φ × 150mm)

Mobile phase A liquid: 0.1% TBAB / water: acetonitrile (9:1)

Solution B: 0.1% TBAB/water: acetonitrile (1:9)

Gradient (B solution)

Initial concentration of B 25%

25% → (30 minutes) → 100% (for 20 minutes)

Detection wavelength 254 nm

Column temperature 40 ° C

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 the concentration described in Table 11. The solution was subjected to high-speed liquid chromatography analysis under the above conditions, and the elution time and peak area were measured. The results are shown in Table 11.

The calibration curve obtained from the concentration of the solution and the measured peak area is represented by the following formula.

The calibration curve of the compound represented by formula (1-6): (peak area) = 72.2 × (concentration)

The calibration curve of the compound represented by the formula (1-7): (peak area) = 76.0 × (concentration)

13.9 mg of the dye (a) was dissolved in acetonitrile to a volume of 50 cm ³ (concentration: 0.278 g/l), and high-speed liquid chromatography analysis was carried out under the above conditions to measure the elution time and the peak area. The compound represented by the formula (1-7) was eluted at a dissolution time of 35.9 minutes, and its peak area was 944,436. The compound represented by the formula (1-6) was eluted at a dissolution time of 37.9 minutes, and its peak area was 1,108,707.

As a result of determining the content ratio of each compound in the dye (a) by the above-mentioned calibration curve, the compound represented by the formula (1-6) / the compound represented by the formula (1-7) = 44.7/55.3.

Synthesis Example 2

A reflux condenser was placed, and a flask in which the funnel and the mixer were dropped was purged with nitrogen gas at 0.02 L/min to obtain a nitrogen atmosphere, and 305 parts by mass of ethyl lactate was charged, and the mixture was heated to 70 ° C with stirring.

Then, 60 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ] decyl acrylate (the compound represented by the formula (I) and the compound represented by the formula (II), mixed at 50:50) 240 parts. Further, the solution was dissolved in 140 parts by mass of ethyl lactate to prepare a solution, and the solution was dropped into a flask kept at 70 ° C for 4 hours using a dropping funnel.

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

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured by the GPC method under the following conditions.

Device: K2479 (made 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 (TOSO)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.

Example 1 [Preparation of coloring curable resin composition]

will

(A) Colorant: 38 parts of C.I. Pigment Green 7 (pigment)

Acrylic pigment dispersant 17 parts

Propylene glycol monomethyl ether acetate 245 parts Mixing, pigment dispersion that fully disperses the pigment with a bead mill

(A) Colorant: Dye (a) (yellow dye) 38 parts

(B) Resin: Resin B1 (solid content conversion) 40 parts

(C) Polymerizable compound: dipentaerythritol hexaacrylate (Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts

(D) Polymerization initiator: N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacurea OXE 01; manufactured by BASF Corporation) 10 parts

(F) Leveling agent: Polyether modified siloxane oil (Toray Silicone SH8400: manufactured by Toray. Dow Corning Co., Ltd.) 0.12 parts

(E) Solvent: ethyl lactate 261 parts

(E) Solvent: propylene glycol monomethyl ether acetate 424 parts

The composition is colored to form a curable resin composition.

[Production of coloring graphics]

The colored curable resin composition was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 square meters, and then baked at 100 ° C for 3 minutes to form a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the mask made of quartz glass was 200 μm, and an exposure amount of 40 mJ/cm ² was observed in an atmosphere using an exposure machine (TME-150 RSK; manufactured by Topcon Co., Ltd.). (365 nm reference) light irradiation. At this time, in the case of the photomask, a photomask which forms a line and a space pattern of 100 μm is used. The composition layer after the light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for development for 60 seconds, and after washing with water, baked in an oven at 230 ° C. Minutes, I have to color the graphics.

[Measurement of film thickness]

The film thickness of the obtained coloring pattern was measured by a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 12.

[Colorimetric evaluation]

The obtained coloring pattern was measured by a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate (x, y) in the XYZ color system of CIE was measured by the characteristic function of the C light source. ) and brightness Y. The results are shown in Table 12.

Example 2

will

(A) Colorant: C.I. Pigment Green 7 (Pigment) 43 parts

Acrylic pigment dispersant 19 parts

Between 272 parts of propylene glycol monomethyl ether acetate, a pigment dispersion in which the pigment is sufficiently dispersed by a bead mill,

(A) Colorant: C.I. Pigment Yellow 138 (Pigment) 17 parts

Acrylic pigment dispersant 5.1 parts

Propylene glycol monomethyl ether acetate 86 parts Mixing, using a bead mill to fully disperse the pigment dispersion, will

(A) Colorant: Dye (a) (yellow dye) 26 parts

(B) Resin: Resin B1 (solid content conversion) 40 parts

(C) Polymeric compound: dipentaerythritol hexaacrylate (Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts

(D) Polymerization initiator: N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one -2-imine (Irgacurea OXE 01; manufactured by BASF) 10 parts

(F) Leveling agent: Polyether modified siloxane oil (Toray Silicone SH8400: manufactured by Toray. Dow Corning Co., Ltd.) 0.13 parts

(E) Solvent: ethyl lactate 256 parts

(E) solvent; propylene glycol monomethyl ether acetate 386 parts The composition is colored to form a curable resin composition.

A colored pattern was produced in the same manner as in Example 1, and film thickness measurement and chromaticity evaluation were carried out.

The results are shown in Table 12.

Example 3 [Preparation of coloring curable resin composition]

will

(A) Colorant: C.I. Pigment Green 7 (Pigment) 44 parts

Acrylic pigment dispersant 20 parts

Propylene glycol monomethyl ether acetate 273 parts Mixing, using a bead mill to fully disperse the pigment dispersion, will

(A) Colorant: C.I. Pigment Yellow 138 (heading) 26 parts

Acrylic pigment dispersant 7.8 parts

Propylene glycol monomethyl ether acetate 129 parts Mixing, using a bead mill to fully disperse the pigment dispersion, will

(A) Colorant: Dye (a) (yellow dye) 18 parts

(B) Resin: Resin B1 (solid content conversion) 40 parts

(C) Polymeric compound: dipentaerythritol hexaacrylate (Kayarad DPHA; manufactured by Nippon Kayaku Co., Ltd.) 60 parts

(D) Polymerization initiator: N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacurea OXE 01; manufactured by BASF Corporation) 10 parts

(F) Leveling agent: Polyether modified siloxane oil (Toray Silicone SH8400: manufactured by Toray. Dow Corning Co., Ltd.) 0.14 parts

(E) Solvent: ethyl lactate 252 parts

(E) Solvent: propylene glycol monomethyl ether acetate 353 parts The composition is colored to form a curable resin composition.

A colored pattern was produced in the same manner as in Example 1, and film thickness measurement and chromaticity evaluation were carried out.

The results are shown in Table 12.

Comparative example 1

will

Colorant: C.I. Pigment Green 7 (loss) 7.5 parts

Colorant: C.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, dispersed pigment dispersion, will

Tree refers to: benzyl methacrylate / methacrylic acid = 70 / 30 (mole ratio) copolymer (acid value is 113; polystyrene-converted weight average molecular weight is 30,000) 28 parts

Polymeric compound: dipentaerythritol hexaacrylate 8 parts

Polymerization initiator: Irgacure 907 (manufactured by BASF Corporation) 2 parts

Surfactant; Megafac F 477 (made by DIC) 2 parts

Solvent: propylene glycol monomethyl ether acetate 126 parts

Solvent: ethyl 3-ethoxypropionate 54 parts The composition is colored to form a curable resin composition.

[Production and evaluation of color coating film]

This colored curable resin composition was applied by a spin coating method on a 5 cm square glass substrate (Eagle XG; manufactured by Corning), and then prebaked at 100 ° C for 3 minutes. After cooling, it was irradiated with an exposure amount (365 nm basis) of 150 mJ/cm ^{2 in} an atmosphere using an exposure machine (TME-150RSK: manufactured by Topcon Co., Ltd.). After light irradiation, it was baked in an oven at 220 ° C for 20 minutes to obtain a colored coating film.

The film thickness measurement and the chromaticity evaluation of the obtained colored coating film were carried out in the same manner as in Example 1.

The results are shown in Table 12.

From the above results, it was confirmed that the coloring curable resin of the present invention was composed. The colored pattern formed by the object has excellent brightness. From this, it is understood that the colored pattern formed of the colored curable resin composition of the present invention is a color filter, and a display device having excellent color performance can be produced.

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

Claims (8)

A colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator; the colorant contains a copper chloride phthalocyanine pigment and a yellow dye, and the content of the yellow dye is relative to the total amount of the colorant. It is 1% by mass or more and 65% by mass or less. The colored curable resin composition according to the above aspect of the invention, wherein the copper chloride indigo pigment is a pigment containing a compound represented by the formula (P1): In the 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]. The colored curable resin composition according to claim 1, wherein the copper chloride indigo pigment is C.I. Pigment Green 7. The colored curable resin composition according to any one of claims 1 to 3, wherein the yellow dye is a yellow azo dye. The colored curable resin composition according to claim 4, wherein the yellow azo dye is a dye containing a compound represented by the formula (1): In the formula (1), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent, and B ⁰ represents a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or may be a monovalent heterocyclic group having 3 to 14 carbon atoms which has a substituent, R ⁵¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or a carbon number 2 to 18 which may have a substituent The thiol group, p1 represents 1 or 2; when p1 is 2, the complex A ⁰ , B ⁰ , R ⁵¹ and R ⁵² may be the same or different from each other, and when p1 is 1, R ⁵² represents a hydrogen atom or may be substituted. a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms, wherein when p1 is 2, R ⁵² represents a divalent saturated hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, the monovalent saturated hydrocarbon group and the divalent -CH ² - contained in the saturated hydrocarbon group may be substituted by -O-, -S-, -CO- or -NR'-, and R' represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms] . The colored curable resin composition according to claim 4, wherein the yellow azo dye is a dye containing a compound represented by the formula (2): [In the formula (2), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, and are contained in Z ¹ , Z ² and Z ³ -CH ² -, which may be substituted by -CO- or -O-; R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, may have a substituent of a monovalent saturated aliphatic hydrocarbon group having 1 to 16 carbon atoms or may a substituent having 2 to 18 carbon atoms, and A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent; and B ¹ and B ² are independently represented There may be a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent. A color filter formed of the color-curable resin composition according to any one of claims 1 to 6. A display device comprising the color filter of claim 7 of the patent application.