KR20220040404A - Coloring curable resin composition, color filter and display device - Google Patents

Abstract

The purpose of the present invention is to provide a colored curable resin composition and the like which can provide a color filter that has an excellent hyperchromic effect. The colored curable resin composition comprises: a colorant (A); a resin (B); a polymerizable compound (C); and a polymerization initiator (D), wherein as the resin (B), a polymer comprises a tertiary carbon-containing (meth)acrylate monomer unit (a1) in excess of 80% by mass out of 100% by mass of a constituent unit.

Description

Colored curable resin composition, a color filter, and a display apparatus TECHNICAL FIELD

[0001] The present invention relates to a colored curable resin composition, a color filter, and a display device.

[0002] In recent years, development of a display display to widen a displayable color gamut is progressing, and as a part of it, a color filter is also required to have a darker color. As a method of thickening a color filter, although the method of raising the colorant density|concentration in a color filter is mentioned, When a colorant density|concentration is made high, performance, such as a pattern shape worsening, is not enough. In addition, in order to have the desired color characteristics, it is necessary to manufacture the color filter as a thick film. Thickening (厚膜化) is not desirable.

[0003] For example, in Patent Document 1, although a colored curable resin composition containing a colorant, a resin, a predetermined polymerizable compound, a polymerization initiator, and a thiol compound is described, to further improve the color thickening (color darkening effect) it is desired

Japanese Patent Laid-Open No. 2020-041154

Accordingly, an object of the present invention is to provide a colored curable resin composition capable of providing a color filter having an excellent hyperchromic effect.

[0006] That is, the colored curable resin composition, color filter, and display device according to the present invention are based on the following points.

[1] It contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),

Colored curable resin composition characterized by containing the polymer which contains a tertiary carbon containing (meth)acrylate monomeric unit (a1) more than 80 mass % in 100 mass % of structural units as resin (B) .

[2] Resin (B) further comprises an unsaturated monomer unit (b1) having an acid group, wherein the unsaturated monomer having an acid group (b1) is at least selected from acrylic acid and methacrylic acid The colored curable resin composition according to [1], which is one type.

[3] The colored curable resin composition according to [1] or [2], wherein the resin (B) has an acid value of more than 80 mgKOH/g and a weight average molecular weight of 9000 or less.

[4] The colored curable resin composition according to any one of [1] to [3], wherein the colorant (A) contains at least a green colorant.

[5] The green colorant, C.I. Pigment Green 58 and C.I. The colored curable resin composition according to [4], which is at least one selected from Pigment Green 59.

[6] The colorant (A) further contains a yellow colorant, and the yellow colorant is C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. The colored curable resin composition according to any one of [1] to [5], which is at least one selected from Pigment Yellow 185.

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

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

ADVANTAGE OF THE INVENTION According to this invention, provision of the colored curable resin composition which can obtain the color filter excellent in the hyperchromic effect becomes possible.

[0008] The colored curable resin composition of the present invention contains a colorant (hereinafter, may be referred to as a colorant (A)) and a resin (hereinafter may be referred to as a resin (B).).

The colored curable resin composition of this invention is a polymeric compound (Hereinafter, it may call a polymeric compound (C).), a polymerization initiator (Hereinafter, it may call a polymerization initiator (D).), a solvent (Hereinafter, it may be called a polymerization initiator.) , a solvent (E) may be included.), and a polymerization initiation assistant (hereinafter, may be referred to as a polymerization initiation assistant (D1).) may be included.

The colored curable resin composition of this invention may contain the leveling agent (Hereinafter, it may call a leveling agent (F).).

In the present invention, the hyperchromic effect means that a difference in color change occurs between the pre-bake coloring composition layer and the post-bake color filter, and the color per predetermined film thickness This is said to be intense.

[0009] The colored curable resin composition according to the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and as the resin (B), contains tertiary carbon It is characterized by containing the polymer which contains a (meth)acrylate monomeric unit (a1) more than 80 mass % in 100 mass % of structural units.

In addition, in this specification, "(meth)acrylate" shows at least 1 sort(s) chosen from the group which consists of an acrylate and a methacrylate. Notations, such as "(meth)acryloyl" and "(meth)acrylic acid", also have the same meaning.

[0010] The compounds exemplified as each component in the present specification may be used alone or in combination of a plurality of types, unless otherwise specified.

[0011] <Colorant (A)>

It is preferable that the colored curable resin composition which concerns on this invention contains a coloring agent (A), and that a coloring agent (A) contains a green coloring agent at least. The green colorant may be any of a pigment and a dye, but is preferably a pigment, more preferably zinc phthalocyanine, still more preferably polyhalogenated zinc phthalocyanine, still more preferably polychlorinated zinc phthalocyanine or polybrominated zinc phthalocyanine. and CI Pigment Green 58, and C.I. Particular preference is given to being selected from pigment green 59.

[0012] The green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is, if necessary, a rosin treatment, an acidic or basic group introduced surface treatment using a pigment derivative, etc., a polymer compound Graft treatment to the surface of the pigment by means of, etc., atomization treatment by sulfuric acid atomization method, etc., cleaning treatment with an organic solvent or water to remove impurities, or removal treatment by ion exchange method for ionic impurities, etc. it may be

[0013] The green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is preferably used in the state of a dispersion uniformly dispersed in a solvent, and the dispersion is a green colorant (preferably zinc It can be obtained by mixing phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) in a solvent. You may mix a dispersing agent as needed.

[0014] The dispersing agent may be any of cationic, anionic, nonionic, and amphoteric dispersants, and a polyester-based, polyamine-based, and acrylic-based dispersing agent is exemplified.

These dispersants may be used independently and may be used in combination of 2 or more type. As a dispersing agent, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), Aji under the trade names. Spa (made by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (made by BYK-Chemie), etc. are mentioned.

As a dispersing agent, from a viewpoint of the dispersibility of a coloring agent, and compatibility with resin (B), you may use resin (B) (preferably resin (B1)) mentioned later.

When using a dispersing agent, the usage-amount becomes like this with respect to 100 mass parts of pigments. Preferably they are 100 mass parts or less, More preferably, they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of a pigment dispersing agent exists in the said range, there exists a tendency for the pigment dispersion liquid which disperse|distributed the pigment uniformly in the solvent to be obtained.

[0015] The solvent is not particularly limited, and the same solvent as the solvent (E) in the colored curable resin composition of the present invention may be mentioned. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxy Butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc. are preferable, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are preferable. , dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, etc. are more preferable.

Although the usage-amount of a solvent is not specifically limited, The solvent may be used so that the solid content concentration in a pigment dispersion liquid can be adjusted to 3-30 mass %, More preferably, it is 5-25 mass %.

[0016] Further, as the colorant (A), a second colorant other than the green colorant (preferably zinc phthalocyanine, more preferably polyhalogenated zinc phthalocyanine) is a yellow colorant, a blue colorant, etc., containing pigments and/or dyes. may be doing It is preferable that a coloring agent (A) further contains a yellow coloring agent.

[0017] Examples of the pigment include organic pigments and inorganic pigments, and compounds classified as pigments in the Color Index (published by The Society of Dyers and Colorists).

As an organic pigment, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 yellow pigments;

C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60;

C.I. Violet pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments other than polyhalogenated zinc phthalocyanine, such as Pigment Green 7 and 36;

and the like.

Among them, the pigment preferably includes at least one selected from the group consisting of a green pigment other than zinc phthalocyanine, a yellow pigment, and a blue pigment, and the blue pigment is preferably included together with the yellow pigment. .

A green colorant (preferably a green pigment) and a blue colorant (preferably a blue pigment) include C.I. Pigment Blue 15:3, 15:6, C.I. Pigment greens 7 and 36 are preferable. A yellow colorant (preferably a yellow pigment) is C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and C.I. It is preferably selected from Pigment Yellow 185. You may use 2 or more types of these pigments.

[0019] The pigment is, if necessary, rosin treatment, surface treatment using a pigment derivative or pigment dispersant introduced with acidic or basic groups, graft treatment to the pigment surface with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc. , washing treatment with an organic solvent or water for removing impurities, or removal treatment of ionic impurities by an ion exchange method or the like may be performed. Moreover, it is preferable that a pigment has a uniform particle diameter. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

As the pigment dispersant, commercially available surfactants can be used, and silicone-based, fluorine-based, ester-based, cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, acrylic-based, etc. Surfactant etc. are mentioned. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, and the like. In addition, as trade names, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by KYOEISHA CHEMICAL Co., LTD.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF JAPAN LTD.), Ajispa (trademark) (made by Ajinomoto Fine-Techno Co., Inc.), Disperbyk (made by BYK-Chemie), etc. are mentioned. These can be used individually, respectively, or can be used in combination of 2 or more type.

[0021] When a pigment dispersant is used, the amount used is preferably 100% by mass or less, and more preferably 1 to 50% by mass relative to the pigment. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

[0022] The dye is not particularly limited, and a known dye may be used, and examples thereof include solvent dyes, acid dyes, direct dyes, mordant dyes, and the like. As a dye, for example, a compound classified as having a color other than a pigment in the color index (published by The Society of Dyers and Colorists), and a dyeing note (SHIKISENSHA CO., LTD. and the known dyes that have been described. In addition, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium (squarylium) ) dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, and nitro dyes. Among these, organic solvent-soluble dyes are preferable.

[0023] The total content of the colorant is 45.5% by mass or more, preferably 46.0% by mass or more, more preferably 46.5% by mass or more, based on the solid content of the colored curable resin composition, from the viewpoint of the darkening effect. , More preferably, it is 65 mass % or less, More preferably, it is 63 mass % or less, More preferably, it is 61 mass % or less.

[0024] The content of the green colorant can be appropriately adjusted so as to achieve a desired chromaticity. From a viewpoint of a hyperchromic effect, with respect to the solid content of all the coloring agents, Preferably they are 35 mass % or more and 99.9 mass % or less. The lower limit of the content rate of a green coloring agent becomes like this. More preferably, it is 40 mass % or more, More preferably, it is 50 mass % or more, More preferably, it is 60 mass % or more. Moreover, the upper limit of the content rate of a green coloring agent becomes like this. More preferably, it is 98 mass % or less, More preferably, it is 95 mass % or less, More preferably, it is 90 mass % or less.

The content rate of the green colorant is preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 55 mass% or less, further preferably with respect to the solid content of the colored curable resin composition from the viewpoint of the darkening effect. is 15 mass % or more and 50 mass % or less, More preferably, they are 20 mass % or more and 45 mass % or less.

[0025] The colorant is C.I. Pigment Green 59 and C.I. In the case of containing both Pigment Green 58, "C.I. Content of Pigment Green 59: C.I. Content of Pigment Green 58”, C.I. Pigment Green 59 and C.I. The content ratio ratio of pigment green 58 should just be the range of 0.1-99.9:99.9-0.1, Preferably it is 1-99:99-1. Such a content rate can be suitably adjusted according to a desired color.

When a green pigment other than zinc phthalocyanine is contained, the amount of green pigment other than zinc phthalocyanine used is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of zinc phthalocyanine, More preferably, it is 10 mass parts or more, 2000 mass parts or less are preferable, 300 mass parts or less are more preferable, and 100 mass parts or less are still more preferable.

[0027] The yellow colorant may be any of a yellow pigment and a yellow dye, and is preferably a yellow pigment.

As for the content rate of all yellow pigment, 5 mass % or more and 40 mass % or less are preferable with respect to the solid content of all coloring agents, More preferably, 10 mass % or more, More preferably, 15 mass % or more, More preferably, 20 mass % or more. % or more.

As for the content rate of all yellow pigments, 1 mass % or more and 30 mass % or less are preferable with respect to solid content of all colored curable resin composition, More preferably, they are 25 mass % or less, More preferably, they are 20 mass % or less.

[0028] The blue colorant may be any of a blue pigment and a blue dye, and is preferably a blue pigment.

As for the content rate of all the blue pigments, 0.1 mass % or more and 30 mass % or less are preferable with respect to solid content of all coloring agents, More preferably, 1 mass % or more and 25 mass % or less, More preferably, 3 mass % or more and 20 mass %. is below.

As for the content rate of all the blue pigments, 1 mass % or more and 30 mass % or less are preferable with respect to solid content of all colored curable resin composition, More preferably, they are 25 mass % or less, More preferably, they are 20 mass % or less.

When the colorant (A) contains both a green colorant and a yellow colorant, the content of the yellow colorant is preferably 1 to 100 parts by mass, more preferably 2 to 80 parts by mass, with respect to 100 parts by mass of the green colorant, More preferably, it is 5-60 mass parts, More preferably, it is 8-40 mass parts.

[0029] The total amount of the colorant (A) is preferably 25 to 65 mass%, more preferably 30 to 60 mass%, still more preferably 35 to 55 mass%, based on 100 mass% of the solid content of the colored curable resin composition. %am.

[0030] <Resin (B)>

Alkali-soluble resin may be sufficient as resin (B) used by this invention. As resin (B), the polymer (B1) which contains a tertiary carbon containing (meth)acrylate monomeric unit (a1) more than 80 mass % in 100 mass % of structural units is contained (henceforth resin ( It is sometimes called B1).).

[0031] Resin (B1) is a resin that does not contain both a monomer unit having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond and a unit derived therefrom.

[0032] The tertiary carbon-containing (meth)acrylate as the tertiary carbon-containing (meth)acrylate unit (a1) is, for example, the following general formula (1):

CH ₂ =C(R)-C(=O)-OC(R ¹ )(R ² )(R ³ ) (1)

(R represents a hydrogen atom or a methyl group. R ¹ , R ² and R ³ represent a monovalent organic group having a carbon atom at a bonding position with a carbon atom, R ¹ , R ² and R At least one of ³ has at least one hydrogen atom at the carbon atom at the bonding position with the carbon atom, among R ¹ , R ² and R ³ , R ¹ and R ² , R ² and R ³ , or R ¹ and R ³ may form a ring as one.).

[0033] R ¹ , R ² and R ³ are the same or different, preferably a hydrocarbon group having 1 to 30 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 15 carbon atoms, still more preferably 1 to carbon atoms A saturated hydrocarbon group having 10 carbon atoms, still more preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. A saturated hydrocarbon group may be sufficient as this hydrocarbon group, and an unsaturated hydrocarbon group may be sufficient as it.

A hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ , R ² and R ³ , a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group , undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetraco straight-chain alkyl groups such as an actual group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, and a triacontyl group;

Isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 3-methylbutyl group, neopentyl group, 1,1-dimethylpropyl group, 2- Methylpentyl group, 3-ethylpentyl group, 2-propylpentyl group, 1-methylpentyl group, 4-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, 2-ethylhexyl group, 1-methylhexyl group Sil group, 1-ethylpentyl group, 1-propylbutyl group, 3-ethylheptyl group, 1-methylheptyl group, 1-ethylhexyl group, 1-propylpentyl group, 1-methyloctyl group, 1-ethylheptyl group, branched-chain alkyl groups such as 1-propylhexyl group, 1-butylpentyl group, 1-methylnonyl group, 1-ethyloctyl group, 1-propylheptyl group and 1-butylhexyl group;

Cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4- Methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethyl cyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group;

alicyclic hydrocarbon groups such as a decahydronaphthyl group, a norbornyl group, an adamantyl group, and a bicyclo[2.2.2]octyl group;

Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5- Dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 4-butyl Phenyl group, 4-pentylphenyl group, 1-naphthyl group, 2-naphthyl group, 6-methyl-2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8- Tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group, anthryl group, 2-dodecylphenyl group, 3-dodecylphenyl group, 4-dodecylphenyl group, peryleneyl group, chrysenyl group, pyrenyl group, etc. An aromatic hydrocarbon group etc. are mentioned.

The hydrocarbon group having 1 to 30 carbon atoms represented by R ¹ , R ² and R ³ may be a combination of two selected from the aforementioned linear alkyl group, branched chain alkyl group, alicyclic hydrocarbon group, and aromatic hydrocarbon group.

Especially, a linear alkyl group, a branched alkyl group, and an alicyclic hydrocarbon group are preferable, and a branched alkyl group and an alicyclic hydrocarbon group are more preferable.

[0035] Examples of the ring that R ¹ and R ² , R ² and R ³ , or R ¹ and R ³ may form as one include the same groups as the alicyclic hydrocarbon group exemplified above.

Specific examples of the tertiary carbon-containing (meth)acrylate unit (a1) include the following structural units (a1-0) to (a1-2).

[0037]

[In formula (a1-0), formula (a1-1) and formula (a1-2),

L ^a01 , L ^a1 and L ^a2 each independently represent an oxygen atom or *-O-(CH ₂ ) _k1 -CO-O-, k1 represents an integer of any one of 1 to 7, and * is - Indicates the bonding position with CO-.

R ^a01 , R ^a4 and R ^a5 each independently represent a hydrogen atom or a methyl group.

R ^a02 , R ^a03 and R ^a04 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group combining them.

R ^a6 and R ^a7 each independently represent an alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group having 3 to 18 carbon atoms, or a group formed by combining them.

m1 represents the integer in any one of 0-14.

n1 represents the integer in any one of 0-10.

n1' represents any integer from 0 to 3.]

[0038] R ^a01 , R ^a4 and R ^a5 are preferably a hydrogen atom.

L ^a01 , L ^a1 and L ^a2 are preferably an oxygen atom or *-O-(CH ₂ ) _k01 -CO-O- (provided that k01 is preferably an integer of any one of 1 to 4; More preferably, it is 1.), More preferably, it is an oxygen atom.

Examples of the alkyl group for R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.

The alicyclic hydrocarbon group for R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 may be either monocyclic or polycyclic. Examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic alicyclic hydrocarbon group include a decahydronaphthyl group, an adamantyl group, a norbornyl group, and the following groups (* indicates a bonding position).

[0039]

[0040] Examples of the group combining an alkyl group and an alicyclic hydrocarbon group in R ^a02 , R ^a03 , R ^a04 , R ^a6 and R ^a7 include, for example, a methylcyclohexyl group, a dimethylcyclohexyl group, a methylnorbornyl group, and a cyclohexylmethyl group. , adamantylmethyl group, adamantyldimethyl group, norbornylethyl group, and the like.

[0041] The number of carbon atoms in the alkyl group in R ^a02 , R ^a03 , and R ^a04 is preferably 1 to 6, more preferably 1 to 4, and still more preferably 1 to 2.

The number of carbon atoms of the alkyl group in R ^a6 and R ^a7 is preferably 1 to 6, more preferably 1 to 4, still more preferably 2 to 3.

The carbon number of the alicyclic hydrocarbon group of R ^a02 , R ^a03 and R ^a04 is preferably 5 to 12, more preferably 5 to 10.

As for the group which combined an alkyl group and an alicyclic hydrocarbon group, it is preferable that the total carbon number which combined these alkyl group and an alicyclic hydrocarbon group is 18 or less.

[0042] R ^a02 and R ^a03 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group.

R ^a04 is preferably an alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group having 5 to 12 carbon atoms, and more preferably a methyl group, ethyl group, cyclohexyl group or adamantyl group.

R ^a6 and R ^a7 are preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and still more preferably an ethyl group or an isopropyl group.

[0043] m1 is preferably an integer from 0 to 3, and more preferably 0 or 1.

n1 is preferably an integer in any one of 0 to 3, More preferably, it is 0 or 1.

n1' is preferably 0 or 1.

[0044] As the structural unit (a1-0), for example, in formulas (a1-0-1) to (a1-0-12) and (a1-0-13) to (a1-0-24) The structural unit represented by any one is mentioned.

[0045]

[0046]

[0047] As the structural unit (a1-1), for example, in formulas (a1-1-1) to (a1-1-4) and (a1-1-5) to (a1-1-8) The structural unit represented by any one is mentioned.

[0048]

[0049]

[0050] As the structural unit (a1-2), any one of formulas (a1-2-1) to (a1-2-6) and (a1-2-7) to (a1-2-12) The structural unit shown is mentioned.

[0051]

[0052]

Among them, the tertiary carbon-containing (meth)acrylate unit (a1) is preferably a structural unit represented by formula (a1-0), and formulas (a1-0-1) to (a1-) 0-24), more preferably a structural unit represented by formulas (a1-0-13) to (a1-0-24), still more preferably a structural unit represented by formulas (a1-0-13) It is still more preferable that it is a structural unit represented by

[0054] The content of the tertiary carbon-containing (meth)acrylate unit (a1) is more than 80% by mass, preferably 80.1% by mass or more, more preferably in 100% by mass of the structural units of the resin (B1). It is 80.2 mass % or more, Preferably it is less than 100 mass %, More preferably, it is 99 mass % or less, More preferably, it is 97 mass % or less, More preferably, it is 95 mass % or less.

[0055] The resin (B) further includes an unsaturated monomer unit (b1) having an acid group, and the unsaturated monomer having an acid group in (b1) is preferably at least one selected from acrylic acid and methacrylic acid. And, it is more preferable that it is acrylic acid.

The content of the unsaturated monomer unit (b1) having an acid group is preferably less than 20 mass%, more preferably 19.9 mass% or less, still more preferably 19.8% by mass, among 100 mass% of the structural units of the resin (B1). It is mass % or less, Preferably it is more than 0 mass %, More preferably, it is 1 mass % or more, 3 mass % or more, or 5 mass % or more.

As the resin (B), the structural unit preferably includes a polymer (B1) composed of a tertiary carbon-containing (meth)acrylate unit (a1) and an unsaturated monomer unit having an acid group (b1) ( Hereinafter, it may be referred to as resin (B1).).

[0058] The resin (B) (preferably resin (B1)) preferably has an acid value of more than 80 mgKOH/g and a weight average molecular weight of 9000 or less.

The acid value of the resin (B1) is preferably more than 80 mgKOH/g, more preferably 85 mgKOH/g or more, still more preferably 95 mgKOH/g or more, still more preferably 105 mgKOH/g or more, preferably It is 300 mgKOH/g or less, More preferably, it is 250 mgKOH/g or less, More preferably, it is 200 mgKOH/g or less.

The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The weight average molecular weight in terms of polystyrene of the resin (B1) is preferably 9000 or less, more preferably 8500 or less, still more preferably 8000 or less, still more preferably 7500 or less, preferably 1000 or more, More preferably, it is 1500 or more, More preferably, it is 2000 or more, More preferably, it is 2500 or more.

[0061] The content of the resin (B1) is preferably 40 to 100% by mass, more preferably 50 to 95% by mass, and still more preferably 60 to 90% by mass in 100% by mass of the resin (B).

The content rate of resin (B1) is in 100 mass % of solid content of colored curable resin composition, Preferably it is 1-50 mass %, More preferably, it is 2-45 mass %, More preferably, 5-40 mass % is still more preferable. Preferably, it is 8-35 mass %.

[0062] The resin (B) may contain a resin (B2) different from the resin (B1) (hereinafter referred to as resin (B2) in some cases). Examples of the resin (B2) include the following resins [K1] to [K6].

resin [K1]; A structural unit derived from at least one (a2) (hereinafter sometimes referred to as “(a2)”) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a cyclic ether having 2 to 4 carbon atoms a copolymer having a structural unit derived from a monomer (b2) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2)”);

resin [K2]; The structural unit derived from (a2), the structural unit derived from (b2), and the monomer (c2) copolymerizable with (a2) (however, it is different from (a2) and (b2).) (hereinafter "(c2)" )", a copolymer having a structural unit derived from );

resin [K3]; a copolymer having the structural unit derived from (a2) and the structural unit derived from (c2);

resin [K4]; a copolymer having a structural unit derived from (c2) and a structural unit obtained by adding (b2) to the structural unit derived from (a2);

resin [K5]; a copolymer having a structural unit derived from (c2) and a structural unit obtained by adding (a2) to the structural unit derived from (b2);

resin [K6]; A copolymer having a structural unit derived from (c2) and a structural unit obtained by adding (a2) to the structural unit derived from (b2) and further adding a carboxylic acid anhydride.

Specific examples of (a2) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic 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 Bicyclo unsaturated compounds containing a carboxy group, such as [2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

Unsaturated mono[(meth)acryl] of polyvalent carboxylic acid having more than divalence, such as succinic acid mono[2-(meth)acryloyloxyethyl] and phthalic acid mono[2-(meth)acryloyloxyethyl] royloxyalkyl]esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from a viewpoint of copolymerization reactivity or a viewpoint of the solubility with respect to the aqueous alkali solution of resin obtained.

[0064] (b2) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond Eggplant refers to a polymerizable compound. As for (b2), the monomer which has a C2-C4 cyclic ether and (meth)acryloyloxy group is preferable.

[0065] As (b2), for example, a monomer (b2-1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b2-1)”), an oxetanyl group and an ethylenically unsaturated bond Monomer (b2-2) (hereinafter sometimes referred to as “(b2-2)”) having a monomer (b2-2) having a tetrahydrofuryl group and an ethylenically unsaturated bond (b2-3) (hereinafter referred to as “(b2-3)” may be the case).

[0066] As (b2-1), for example, a monomer (b2-1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b2-1-1)” monomer (b2-1-2) (hereinafter, sometimes referred to as "(b2-1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

As (b2-1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethyl glycidyl (meth) acrylate, glycidyl vinyl ether , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzylglycidyl ether Cydyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyl) Oxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) ) styrene and the like.

[0068] As (b2-1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, Seroxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl ( meth)acrylate (eg, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (eg, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by formula (I) and The compound etc. which are represented by Formula (II) are mentioned.

[0069]

[In formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group .

X ^a and X ^b represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S-, or *-R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, and 1-hydroxy group. and a hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

R ^a and R ^b preferably include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

[0072] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, A hexane-1,6-diyl group etc. are mentioned.

As X ^a and X ^b , Preferably, a single bond, a methylene group, an ethylene group, *-CH ₂ -O- and *-CH ₂ CH ₂ -O- are mentioned, More preferably, a single bond, *- CH ₂ CH ₂ -O- (* indicates a bond with O).

[0073] Examples of the compound represented by formula (I) include compounds represented by any one of formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15) ) is preferable, and a compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is more preferable.

[0074]

[0075]

[0076] Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among them, formulas (II-1), (II-3), (II-5), (II-7), (II-9), or (II-11) to (II-15) ) is preferable, and the compound represented by Formula (II-1), Formula (II-7), Formula (II-9) or Formula (II-15) is more preferable.

[0077]

[0078]

[0079] The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used together, their content ratio [the compound represented by the formula (I): the compound represented by the formula (II)] is on a molar basis, Preferably it is 5:95-95:5, More preferably, it is 20:80-80:20.

[0080] As (b2-2), a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (b2-2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane , 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3- Methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

As (b2-3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b2-3) include tetrahydrofurfuryl acrylate (eg, Viscoat V#150, manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD), tetrahydrofurfuryl methacrylate, and the like.

[0082] As (b2), it is preferable that it is (b2-1) from the viewpoint that the reliability of the obtained color filter, such as heat resistance and chemical resistance, can be further improved. Furthermore, (b2-1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

[0083] As (c2), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the technical field, as a common name, "dicyclofentanyl (meth) acryl Also called "tricyclodecyl (meth) acrylate" in some cases), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (the relevant technical field) In , it is commonly called "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, (meth)acrylic acid esters such as allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybi Cyclo[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 bicyclo unsaturated compounds such as -2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, 2-hydroxyethyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1] Hept-2-ene and the like are preferable.

[0084] In the resin [K1], the ratio of the structural units derived from each of the total structural units constituting the resin [K1],

the structural unit derived from (a2); 2-60 mol%

the structural unit derived from (b2); 40-98 mol%

It is preferable that

the structural unit derived from (a2); 10-50 mol%

the structural unit derived from (b2); 50-90 mol%

It is more preferable that

When the ratio of the structural unit of resin [K1] exists in said range, the storage stability of colored curable resin composition, developability at the time of forming a colored pattern, and solvent resistance of the color filter obtained ) can be excellent.

[0085] Resin [K1] is, for example, described in the document "Experimental Methods for Polymer Synthesis" (published by Takayuki Otsu, Kagaku-Dojin Publishing Company, INC. First Edition First Edition March 1, 1972) It can be prepared by referring to the method and the cited literature described in the document.

[0086] Specifically, a predetermined amount of (a2) and (b2), a polymerization initiator, a solvent, etc. are put into a reaction vessel, for example, by replacing oxygen with nitrogen, to create a deoxygenated atmosphere, and stirring (攪拌) while heating and heat-retaining is mentioned. In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, Those normally used in the said field|area can be used. For example, as a polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) What is necessary is just to melt|dissolve each monomer as a solvent, The solvent etc. which are mentioned later as a solvent (E) of the colored curable resin composition of this invention are mentioned.

In addition, the obtained copolymer may use the solution after the reaction as it is, may use a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as re-precipitation. ) may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the colored curable resin composition of the present invention, so the colored curable resin of the present invention The manufacturing process of the composition can be simplified.

[0088] In the resin [K2], the ratio of the structural units derived from each of the total structural units constituting the resin [K2],

the structural unit derived from (a2); 2-45 mol%

the structural unit derived from (b2); 2-95 mol%

the structural unit derived from (c2); 1-65 mol%

It is preferable that

the structural unit derived from (a2); 5-40 mol%

the structural unit derived from (b2); 5-80 mol%

the structural unit derived from (c2); 5-60 mol%

It is more preferable that

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter are excellent can do.

[0089] The resin [K2] can be produced, for example, in the same manner as described for the production method of the resin [K1].

[0090] In the resin [K3], the ratio of the structural units derived from each of the total structural units constituting the resin [K3],

the structural unit derived from (a2); 2-60 mol%

the structural unit derived from (c2); 40-98 mol%

It is preferable that

the structural unit derived from (a2); 10-50 mol%

the structural unit derived from (c2); 50-90 mol%

It is more preferable that

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

[0091] Resin [K4] obtains a copolymer of (a2) and (c2), and (a2) has a cyclic ether having 2 to 4 carbon atoms and/or a carboxylic acid It can be prepared by adding to anhydride.

First, the copolymer of (a2) and (c2) is prepared in the same manner as described as the method for producing the resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was illustrated by resin [K3].

[0092] Next, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a2) in the copolymer is reacted with the cyclic ether having 2 to 4 carbon atoms in (b2).

Following the preparation of the copolymers of (a2) and (c2), the atmosphere in the flask is substituted with air from nitrogen, and (b2), a reaction catalyst of a carboxylic acid or carboxylic anhydride and a cyclic ether (such as tris(dimethyl Resin [K4] can be prepared by putting aminomethyl) phenol, etc.) and a polymerization inhibitor (eg hydroquinone, etc.) in a flask and reacting at 60 to 130° C. for 1 to 10 hours.

As for the usage-amount of (b2), 5-80 mol is preferable with respect to 100 mol (a), More preferably, it is 10-75 mol. By setting it as this range, the storage stability of colored curable resin composition, developability at the time of forming a pattern, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the pattern obtained can become favorable. Since the reactivity of the cyclic ether is high and unreacted (b2) hardly remains, as (b2) used for the resin [K4], (b2-1) is preferable, and (b2-1-1) is more preferable. Do.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a2), (b2), and (c2). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a2), (b2), and (c2).

Reaction conditions, such as a preparation method, reaction temperature, and time, can be suitably adjusted in consideration of manufacturing equipment, the amount of heat generated by polymerization, and the like. In addition, similarly to polymerization conditions, the preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

[0093] The resin [K5] is the first step, in the same manner as the above-described method for producing the resin [K1], to obtain a copolymer of (b2) and (c2). As for the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, and what was extracted as a solid (powder) by methods, such as reprecipitation, may be used.

The ratio of the structural units derived from (b2) and (c2) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer,

the structural unit derived from (b2); 5-95 mol%

the structural unit derived from (c2); 5-95 mol%

It is preferable that

the structural unit derived from (b2); 10-90 mol%

the structural unit derived from (c2); 10-90 mol%

It is more preferable that

[0094] Further, under the same conditions as in the production method of the resin [K4], the carboxylic acid or carboxylic acid of (a2) in the cyclic ether derived from (b2) possessed by the copolymers of (b2) and (c2) By reacting the acid anhydride, the resin [K5] can be obtained.

As for the usage-amount of (a2) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (b2). Since the reactivity of the cyclic ether is high and unreacted (b2) hardly remains, as (b2) used for the resin [K5], (b2-1) is preferable, and (b2-1-1) is more preferable. Do.

[0095] The resin [K6] is a resin in which a carboxylic acid anhydride is further reacted with the resin [K5]. A carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction between the cyclic ether and the carboxylic acid or carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. are mentioned. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amounts of (a2).

[0096] Specifically, as the resin (B2), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylic resin [K1], such as a rate/(meth)acrylic acid copolymer; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decylacrylate/(meth)acrylic acid/N- Resin [K2], such as a cyclohexyl maleimide/2-hydroxyethyl (meth)acrylate copolymer and 3-methyl-3- (meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; Resin [K3], such as (meth)acrylic acid ester/(meth)acrylic acid copolymer, benzyl (meth)acrylate/(meth)acrylic acid copolymer, and styrene/(meth)acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, and glycidyl (meth) to a tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer ) Resin to which acrylate is added, resin [K4], such as a resin which added glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer; Tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymer with (meth)acrylic acid, tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate resin [K5] such as a resin obtained by reacting (meth)acrylic acid with a copolymer; and resin [K6] such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride. there is.

Especially, as resin (B2), resin [K1] and resin [K2] are preferable, and resin [K1] is especially preferable.

[0097] The weight average molecular weight of the resin (B2) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30,000, still more preferably 9,500 to 30,000. . When molecular weight exists in said range, the solubility with respect to the developing solution of an unexposed part is high, and there exists a tendency for the residual film rate and hardness of the pattern obtained also to be high.

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of resin (B2) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The solid content acid value of the resin (B2) is preferably 85 mgKOH/g or more, more preferably 100 mgKOH/g or more, and still more preferably 110 mgKOH/g or more. Moreover, solid content acid value becomes like this. Preferably it is 200 mgKOH/g or less, More preferably, it is 180 mgKOH/g or less, More preferably, it is 160 mgKOH/g or less. There exists a tendency for the coloring pattern with a favorable shape to be obtained from colored curable resin composition as solid content acid value of resin (B2) is said range. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

[0099] The content of the resin (B2) is preferably 0 to 60 mass%, more preferably 5 to 50 mass%, still more preferably 10 to 40 mass%, in 100 mass% of the resin (B). am.

The content rate of resin (B2) in 100 mass % of solid content of colored curable resin composition, Preferably it is 1-40 mass %, More preferably, it is 2-35 mass %, More preferably, it is 3-30 mass %. .

[0100] The content of the resin (B) (preferably the content of the resin (B1) and the resin (B2)) is preferably 5 to 50 mass% in 100 mass% of the solid content of the colored curable resin composition, more preferably Preferably it is 10-40 mass %, More preferably, it is 15-30 mass %. When content of resin (B) exists in said range, there exists a tendency for the solubility with respect to the developing solution of an unexposed part to be high.

[0101] <Polymerizable compound (C)>

The polymerizable compound (C) is a compound capable of polymerization with active radicals and/or acids generated from the polymerization initiator (D). As a polymeric compound (C), the compound which has a polymerizable ethylenically unsaturated bond and a hydroxyl group is mentioned.

[0102] Specific examples of the polymerizable compound (C) include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene glycol modified pentaerythritol tri (meth)acrylate, propylene glycol modified pentaerythritol triacrylate, trimethylolpropane di(meth)acrylate, ethylene glycol modified trimethylolpropane di(meth)acrylate, ethylene glycol modified glycerin di(meth)acrylate, Propylene glycol modified glycerin di(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ethylene glycol modified ditrimethylolpropane tri(meth)acrylate, propylene glycol modified ditrimethylolpropane triacrylate, dipentaeryth lytol pentaacrylate,

Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) Acrylate, tetrapentaerythritol deca (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipenta Erythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, capro and lactone-modified dipentaerythritol hexa(meth)acrylate.

[0103] The content of the polymerizable compound (C) is preferably 1 mass % or more, more preferably 2 mass % or more, still more preferably 3 mass % or more, with respect to the total amount of solid content of the colored curable resin composition. Moreover, it is preferable that it is 50 mass % or less, More preferably, it is 40 mass % or less, More preferably, it is 30 mass % or less.

[0104] <Polymerization initiator (D)>

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

[0105] The O-acyloxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond.

[0106]

[0107] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfa). Nylphenyl) octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-a2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl｝-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- (2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H- Carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2- immigration can be Commercially available products such as Irgacure OXE01, OXE02 (above, manufactured by BASF), N-1919 (made by ADEKA CORPORATION), and PBG-327 (manufactured by Changzhou Tronly New Electronic Materials) may be used. Among them, the O-acyloxime compound is N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl) Octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and N-acetyloxy-1-(4 -Phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine is preferably at least one selected from the group consisting of, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1 At least one selected from the group consisting of -one-2-imine and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine is more preferable. With these O-acyl oxime compounds, a color filter with high brightness can be obtained.

[0108] The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[0109]

[0110] Examples of the compound having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino- 1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) phenyl]butan-1-one. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

As the compound having a partial structure represented by formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2) -Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, an oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one; α,α-diethoxyacetophenone and benzyl dimethyl ketal.

From a viewpoint of a sensitivity, as an alkylphenone compound, the compound which has a partial structure represented by Formula (d2) is preferable.

[0111] As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran) -2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5 -triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis( trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

[0112] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. You may use commercial items, such as Irgacure (trademark) 819 (made by BASF).

[0113] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, Japanese Patent Application Laid-Open Nos. H06-75372, H06-75373, etc.), 2,2' -bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra( Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, Japanese Patent Publication Nos. S48-38403 and S62-174204), 4,4 and biimidazole compounds in which the phenyl group at the ',5,5'-position is substituted with a carboalkoxy group (see, for example, Japanese Patent Application Laid-Open No. H07-10913, etc.).

[0114] Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, benzophenone compounds such as 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. are mentioned. It is preferable to use these in combination with the polymerization initiation adjuvant (D1) (especially amines) mentioned later.

[0115] As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene Sulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene Onium salts, such as a sulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

[0116] The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound. And the polymerization initiator containing an O- acyl oxime compound is more preferable.

[0117] The content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass, with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is more than part and 20 mass parts or less. When content of a polymerization initiator (D) exists in said range, since it can become highly sensitive and exposure time can be shortened, productivity of a color filter improves.

[0118] <Polymerization initiation aid (D1)>

The polymerization initiation adjuvant (D1) is a compound or sensitizer used in order to accelerate|stimulate the polymerization of the polymeric compound which superposition|polymerization was started by a polymerization initiator. When a polymerization initiator auxiliary (D1) is included, it is used in combination with a polymerization initiator (D).

Examples of the polymerization initiation auxiliary (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound. Especially, a thioxanthone compound is preferable. You may contain 2 or more types of polymerization initiation adjuvant (D1).

[0119] As the amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino benzoate isoamyl, benzoate 2-dimethylaminoethyl, 4 -Dimethylaminobenzoate 2-ethylhexyl, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4,4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EAB-F (made by HODOGAYA CHEMICAL CO., LTD.).

[0120] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, 10-dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

[0121] As the thioxanthone compound, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- Propoxythioxanthone etc. are mentioned.

[0122] As the carboxylic acid compound, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanyl Acetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

[0123] The content of the polymerization initiation auxiliary (D1) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C1). am. When the amount of the polymerization initiation auxiliary (D1) is within this range, a coloring pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

[0124] <Solvent (E)>

It is preferable that the colored curable resin composition of this invention contains a solvent (E). As the solvent (E), 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-) , ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0125] As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone, and the like.

[0126] As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetra Hydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol and Methylanisole etc. are mentioned.

[0127] As the ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy methyl propionate, 3-methoxy ethyl propionate, 3-e Methyl oxypropionate, 3-ethoxy ethyl propionate, 2-methoxy methyl propionate, 2-methoxy ethyl propionate, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy -2-methylpropionate, 2-ethoxy-2-methylpropionate ethyl, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, etc. are mentioned.

[0128] As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentane on, cyclopentanone, cyclohexanone, isophorone, and the like.

[0129] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0130] The solvent (E) may be used in combination of two or more.

From a viewpoint of applicability|paintability and drying property, the organic solvent whose boiling point in 1 atm is 120 degreeC or more and 180 degrees C or less is preferable. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy ethyl propionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxy Butyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, and 3-ethoxypropionate ethyl are more preferable.

The content of the solvent (E) is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the colored curable resin composition. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass %, More preferably, it is 8-25 mass %. When content of a solvent (E) exists in said range, since the flatness at the time of application|coating becomes favorable and color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

[0132] <Leveling agent (F)>

As a leveling agent (F), a silicone type surfactant, the silicone type surfactant etc. which have a silicone type surfactant, a fluorine type surfactant, and a fluorine atom are mentioned. These may have a polymerizable group in a side chain.

[0133] Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like.

[0134] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Limited), Megapac (registered trademark) F142D, Megapac F171, Megapac F172, Megapac F173, Megapac F177, Megapac F183, Megapac F554, Megapac R30, Megapac RS-718-K (manufactured by DIC CORPORATION), eftop (registered trademark) EF301, eftop EF303, eftop EF351, eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd. manufactured), Sufflon (registered trademark) S381, Suplon S382, Sufflon SC101, Sufflon SC105 (manufactured by AGC Inc., formerly manufactured by Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Genkyusho) manufacture) and the like.

[0135] Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Megapac BL20, Megapac F475, Megapac F477, and Megapac F443 (manufactured by DIC CORPORATION).

[0136] The content of the leveling agent (F) is, for example, 0.001 mass% or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, more preferably 0.005 to the total amount of the colored curable resin composition. They are mass % or more and 0.05 mass % or less. In addition, content of the said pigment dispersant is not contained in this content. When the content rate of a leveling agent (F) exists in said range, the flatness of a color filter can be made favorable.

[0137] <Method for producing dispersion>

The coloring agent (A) may be dispersed in a dispersing agent and a solvent (E) to form a dispersion.

The dispersant is preferably one or both of the acrylic dispersant and the resin (B1), and more preferably both the acrylic dispersant and the resin (B1).

The content rate of a coloring agent (A) becomes like this in 100 mass % of dispersion liquids, Preferably it is 1-25 mass %, More preferably, it is 2-20 mass %.

The content rate of resin (B1) is preferably 1-20 mass % in 100 mass % of dispersion liquids, More preferably, it is 2-15 mass %.

The content rate of an acrylic dispersing agent becomes like this in 100 mass % of dispersion liquids, Preferably it is 0.1-10 mass %, More preferably, it is 0.5-8 mass %.

[0138] <Method for producing colored curable resin composition>

The colored curable resin composition of this invention contains a coloring agent (A), resin (B), a polymeric compound (C), and a polymerization initiator (D), Furthermore, as needed, a solvent (E) and a leveling agent (F) ), polymerization initiation auxiliary (D1), and other components can be mixed.

A coloring agent (A) can be mixed as said dispersion liquid.

[0139] <Method for manufacturing color filter>

As a method of manufacturing a color filter from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithography method is a method of applying the colored curable resin composition to a substrate, drying it to form a colored composition layer, and then exposing the colored composition layer through a photomask to light and developing. The photolithographic method WHEREIN: The colored coating film which is hardened|cured material of the said coloring composition layer can be formed by not using a photomask at the time of exposure, and/or not developing. The color filter of the present invention may be obtained by pre-baking of the colored curable resin composition (colored composition layer), exposure of the colored composition layer (colored coating film), development of the colored coating film (colored pattern), and post-baking of the colored pattern, As needed, development of a colored coating film may be abbreviate|omitted and it may be obtained by post-baking of a colored coating film.

[0140] As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, silica-coated soda lime glass, etc., a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicone, the substrate What formed a thin film of aluminum, silver, silver/copper/palladium alloy, etc. on it is used. On these board|substrates, another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed. Moreover, you may use the board|substrate which surface-treated by 1,1,1,3,3,3-hexamethyldisilazane etc. on the said board|substrate.

[0141] Formation of each color pixel by the photolithography method can be performed in a known or customary device or condition. For example, it can be produced as follows.

First, after apply|coating colored curable resin composition on a board|substrate, volatile components, such as a solvent, are removed and dried by heat-drying (pre-bake) and/or drying under reduced pressure, and a smooth coloring composition layer is obtained.

Examples of the coating method include a spin coating method, a slit coating method, and a slit-and-spin coating method.

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is between 10 seconds - 5 minutes, and it is more preferable that they are between 30 seconds - 3 minutes.

When drying under reduced pressure, it is preferable to carry out under a pressure of 50 to 150 Pa at a temperature range of 20 to 25°C.

The film thickness of the coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the color filter made into the objective.

[0142] Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern to obtain a colored coating film. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light whose wavelength is 250-450 nm is preferable. For example, light of less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. . Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

[0143] Since it is possible to uniformly irradiate a parallel light beam to the entire exposure surface and perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed, a mask aligner (proximity exposure machine) and a stepper (reduced It is preferable to use an exposure apparatus such as a projection exposure machine).

A coloring pattern is formed on a board|substrate by making a developing solution contact and developing the colored coating film after exposure. By development, the unexposed portion of the colored coating film is dissolved in the developer and removed. As a developing solution, the aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, and tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of these alkaline compounds is preferably 0.01 to 10 mass%, more preferably 0.03 to 5 mass%. Moreover, the developing solution may contain surfactant.

The developing method may be any of a puddle method, a dipping method, and a spray method. In addition, you may incline a board|substrate at an arbitrary angle at the time of image development.

After development, it is preferable to wash with water.

Moreover, it is preferable to post-baking to the obtained coloring pattern. 80-250 degreeC is preferable, as for post-baking temperature, 100-250 degreeC is more preferable, 150-250 degreeC is still more preferable, 160-235 degreeC is still more preferable. The post-baking time is preferably between 1 and 120 minutes, more preferably between 2 and 120 minutes, still more preferably between 10 and 60 minutes, still more preferably between 10 and 30 minutes.

[0144] Since the obtained colored coating film and the colored pattern have an effect on adjacent pixels, it is preferable that the thickness be as thin as possible. In particular, in the case of a thick film, when a liquid crystal panel is manufactured, the light from the light source may leak through pixels of two or more colors. there is a risk of throwing it away. The thickness of the colored coating film and the colored pattern is, for example, preferably 4 µm or less or 3 µm or less, more preferably 2.8 µm or less, still more preferably 2.5 µm or less, still more preferably 2.3 µm or less. Although the lower limit of the film thickness of a colored coating film and a coloring pattern is not specifically limited, Usually, it is 0.1 micrometer or more, Preferably it is 0.2 micrometer or more, 0.5 micrometer or more, or 1 micrometer or more, and 1.5 micrometers or more may be sufficient.

[0145] The color filter has a film thickness of 1 to 4 μm (preferably 1 to 3 μm, more preferably 2.8 μm or less, still more preferably 2.5 μm or less, still more after post-baking at 230° C. for 30 minutes) Preferably it is formed so that it may become 2.3 micrometers or less).

[0146] By using the colored curable resin composition of the present invention, it is possible to manufacture a color filter that particularly satisfies darkening. This color filter is useful as a color filter used for a display device (For example, a liquid crystal display device, organic electroluminescent device, electronic paper, etc.) and a solid-state image sensor.

[Example]

[0147] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples from the beginning, and by adding appropriate changes within the range that can be suitable for the purpose described before and after It is of course possible to implement, and all of these are included in the technical scope of the present invention. In addition, in the following, unless otherwise indicated, "part" means "mass part" and "%" means "mass %".

[0148] Synthesis Example 1

100 parts by mass of propylene glycol monomethyl ether acetate was put into a flask equipped with a stirring blade, a reflux cooling tube, a thermometer, and a dripping funnel, and it was heated at 90°C. A solution in which 81 parts by mass of t-butyl acrylate, 19 parts by mass of acrylic acid, 15 parts by mass of azobis(isobutyronitrile), and 54 parts by mass of propylene glycol monomethyl ether acetate were mixed was continuously dripped into the flask with a dropping funnel. did The temperature inside the flask was maintained at 90±1° C. during the dropping of the mixed solution, and the dropping was completed in 3 hours. After completion of the dropwise addition, the flask internal temperature was set to 90±1° C. and reacted for 3 hours, then the flask internal temperature was raised to 105 to 110° C. and reacted for additional 1.5 hours. A coalescing (resin B1) solution was obtained (hereinafter, sometimes referred to as a resin solution (B1)). The resulting copolymer had a weight average molecular weight (Mw) of 6100 and a solid content acid value of 131 mgKOH/g.

[0149] Synthesis Example 2

In a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was poured into the flask, replaced with a nitrogen atmosphere, 362 parts by mass of propylene glycol monomethyl ether acetate was put, and the mixture was heated to 80°C while stirring. Then, 58 parts by mass of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl The mixed solution of 167 mass parts of mixtures of acrylates (content ratio is 1:1 by molar ratio), 65 mass parts of 2-ethylhexyl acrylates, and 111 mass parts of propylene glycol monomethyl ether acetate was dripped over 5 hours. On the other hand, the mixed solution which melt|dissolved 27 mass parts of 2, 2- azobis (2, 4- dimethylvaleronitrile) in 210 mass parts of propylene glycol monomethyl ether acetate was dripped over 6 hours. After completion of the dropwise addition, the temperature was maintained at 80° C. for 5.5 hours, then cooled to room temperature to obtain a copolymer (resin B2) solution having a type B viscosity (23° C.) of 43 mPa·s and a solid content of 29.8 mass% (hereinafter, a resin solution ( B2) is sometimes called.). The resulting copolymer had a solid content acid value of 149 mgKOH/g, a weight average molecular weight (Mw) of 11220, and a degree of dispersion of 2.25.

[0150] Measurement of the polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained in the above synthesis example was performed using the GPC method under the following conditions.

Device ; HLC-8120GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

column temperature; 40℃

solvent; THF

flow rate ; 1.0mL/min

Test solution solid content concentration; 0.001 to 0.01 mass %

injection volume ; 50 μL

detector ; RI

standard for calibration; TSK STANDARD POLYSTYRENE

F-40, F-4, F-288, A-2500, A-500

(manufactured by TOSOH CORPORATION)

[0151] [Preparation of dispersion]

Dispersions (A-1) to (A-3) were prepared by mixing the following components, respectively, and sufficiently dispersing the pigment using a bead mill. As the resins (B1) to (B2), the above resin solutions (B1) to (B2) were used.

[0152] [Preparation of dispersion (A-1)]

C.I. Pigment Green 58 14.0 copies

1.9 parts of acrylic pigment dispersant

Resin (B2) (in terms of solid content) 6.5 parts

Propylene glycol monomethyl ether acetate 77.6 parts

[0153] [Preparation of dispersion (A-2)]

C.I. Pigment Green 58 14.0 copies

3.3 parts of acrylic pigment dispersant

Resin (B1) (in terms of solid content) 5.6 parts

Propylene glycol monomethyl ether acetate 77.1 parts

[0154] [Preparation of dispersion (A-3)]

C.I. Pigment Yellow 150 12.0 parts

5.4 parts of acrylic pigment dispersant

Resin (B2) (in terms of solid content) 4.2 parts

Propylene glycol monomethyl ether acetate 78.4 parts

[0155] Example 1 and Comparative Example 1

[Preparation of colored curable resin composition]

The components of Table 1 were mixed, and the colored curable resin composition was obtained.

[0156] [Table 1]

[0157] In Table 1, each component is as follows. In addition, the usage-amount in a table|surface shows the usage-amount of the following components.

Dispersions (A-1) to (A-3): the dispersions prepared above

Resin (B1): the copolymer solution obtained in Synthesis Example 1

Resin (B2): the copolymer solution obtained in Synthesis Example 2

Polymeric compound (C): Dipentaerythritol polyacrylate (A-9570W; Shin-Nakamura Chemical Co., Ltd. make)

Polymerization initiator (D): Irgacure (trademark) OXE-03; The BASF company make; The compound represented by formula (d1-24)

[0158]

Solvent (E): Propylene glycol monomethyl ether acetate

Leveling agent (F): polyether-modified silicone oil (SH8400; manufactured by Dow Corning Toray Co., Ltd., propylene glycol monomethyl ether acetate solution having a solid content of 10%)

[0159] <Production of color filter>

On a 2-inch square glass substrate (Eagle XG; manufactured by Corning Incorporated), a colored curable resin composition was applied by spin coating, and then pre-baked at 100° C. for 3 minutes to form a colored composition layer. After standing to cool, the interval between the substrate on which the coloring composition layer is formed and the quartz glass photomask is 100 μm, and using an exposure machine (TME-150 RSK; manufactured by TOPCON CORPORATION), in an atmospheric atmosphere, 150 mJ/cm ² Light was irradiated with an exposure dose (based on 365 nm). As a photomask, the thing in which the 50 micrometers line-and-space pattern was formed was used. The colored coating film after irradiation with light was developed by immersing it in an aqueous developer solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24°C for 60 seconds, washing with water, and then in an oven Post-baking was performed at 230 degreeC for 20 minutes, and the color filter was obtained.

[0160] [Film thickness measurement]

About the obtained color filter, the film thickness FT (micrometer) was measured using the film thickness measuring apparatus (DEKTAK3; Japan Vacuum Engineering Co., Ltd. make).

[0161] [Chromaticity measurement]

For the obtained color filter, spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the xy chromaticity coordinates in the XYZ color system of CIE using the characteristic function of C light source ( x, y) were measured. The xy chromaticity coordinates were measured about the coloring composition layer after a pre-baking and the color filter after a post-baking, and (DELTA)x and (DELTA)y were computed with the following formula|equation. When ?x and ?y were determined, the film thicknesses of Example 1 and Comparative Example 1 were the same.

Δx = (x value of color filter after post-baking) - (x value of coloring composition layer after pre-baking)

Δy = (y-value of the color filter after post-baking) - (y-value of the coloring composition layer after pre-baking)

For example, in a green region, it can be said that the darkening effect after pre-baking and post-baking is high, so that the absolute values of ?x and ?y are larger.

[0162] The colored curable resin composition of the present invention can be suitably used for manufacturing a color filter, a display device, and a solid-state image sensor.

Claims (8)

It contains a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),
As resin (B), the polymer which contains a tertiary carbon containing (meth)acrylate monomeric unit (a1) more than 80 mass % in 100 mass % of structural units is contained, Colored curable resin composition characterized by the above-mentioned . The method of claim 1,
The resin (B) further contains an unsaturated monomer unit (b1) having an acid group, and the unsaturated monomer having an acid group as (b1) is at least one selected from acrylic acid and methacrylic acid. Curable resin composition. 3. The method of claim 1 or 2,
Resin (B) has an acid value of more than 80 mgKOH/g and a weight average molecular weight of 9000 or less colored curable resin composition. 4. The method according to any one of claims 1 to 3,
Coloring curable resin composition in which a coloring agent (A) contains a green coloring agent at least. 5. The method of claim 4,
The colored curable resin composition whose green coloring agent is at least 1 sort(s) chosen from CI pigment green 58 and CI pigment green 59. 6. The method according to any one of claims 1 to 5,
The colorant (A) further contains a yellow colorant, and the yellow colorant is at least one selected from CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Yellow 185. Colored curable resin composition. The color filter formed from the colored curable resin composition in any one of Claims 1-6. A display device comprising the color filter according to claim 7 .