KR20190036196A - Radiation sensitive composition, coloring composition, cured film, insulating film and process for forming the same, spacer, color filter, method for producing spacer and color filter, and liquid crystal display device - Google Patents

Abstract

The present invention is to provide a radiation-sensitive composition having excellent various performances such as focus margin properties and reworkability, and capable of easily forming a pattern as an insulating film, a spacer and a color filter. In addition, the radiation-sensitive composition comprises: [A] a copolymer comprising (a1) a structural unit having a carboxyl group, (a2) a structural unit having an epoxy group, and (a3) a structural unit having a styrene derivative compound; [B] a polymerizable unsaturated compound; [C] a compound represented by specific chemical formula; and a solvent.

Description

TECHNICAL FIELD [0001] The present invention relates to a radiation sensitive composition, a coloring composition, a cured film, an insulating film and a method of manufacturing the same, a spacer and a color filter, a method of manufacturing the same, and a liquid crystal display , SPACER, COLOR FILTER, METHOD FOR PRODUCING SPACER AND COLOR FILTER, AND LIQUID CRYSTAL DISPLAY DEVICE}

TECHNICAL FIELD The present invention relates to a radiation sensitive composition, a coloring composition and a cured film, an insulating film, a spacer, a color filter, a method of manufacturing the same, and a liquid crystal display element, and more particularly to a liquid crystal display panel, A spacer, a color filter, a method of manufacturing the same, and a display device comprising the insulating film, the spacer, and the color filter.

BACKGROUND ART [0002] For a liquid crystal display element, a radiation sensitive composition having excellent resolution as a display panel has been improved in performance has been used.

In addition, the structure of the liquid crystal display element is complicated with the enhancement of the performance of the display panel.

As the structure of the liquid crystal display element is complicated as described above, a decrease in production efficiency becomes a problem.

Japanese Patent Publication No. 2016-505655 Japanese Patent Application Laid-Open No. 2014-194007

SUMMARY OF THE INVENTION The present invention has been made in view of the problems of the prior art described above and has an object of providing a curable resin composition which is excellent in various performances such as focus margin and reworkability, And to provide a composition.

The present inventors have conducted intensive studies to solve the above problems. As a result, it has been found that the above problems can be solved by the radiation sensitive composition having the following constitution, and the present invention has been completed.

That is, the present invention relates to, for example, the following [1] to [14].

In the present specification, the term "(meth) acrylic" means "acrylic" and / or "methacryl".

[1] [A] (a1) a structural unit having a carboxyl group,

        (a2) a structural unit having an epoxy group,

        (a3) a structural unit having a styrene derivative compound

        , ≪ / RTI >

    [B] a polymerizable unsaturated compound,

    [C] a compound represented by the following formula (1) or (2), and

    menstruum

    ≪ / RTI >

(In the formula (1), R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a heterocyclic group, or a (meth) And n represents 0 to 1.

In the formula (2), R ₄ represents a hydrogen atom, a halogen atom, a nitro group, a thiophenecarboxyaldehyde group or a tolualdehyde group. R ₅ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. R ₆ represents an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a heterocyclic ring or a (meth) acryloyl group.

[2] The method according to the above [1]

The copolymer of [A]

(a1) 3 to 30 mass% of a structural unit having a carboxyl group,

(a2) 20 to 60% by mass of a structural unit having an epoxy group,

(a3) 10 to 77 mass% of a structural unit having a styrene derivative compound

≪ / RTI >

[3] The method according to the above [1] or [2]

Wherein the structural unit having an epoxy group in the [A] (a2) is at least one selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, And cetane (meth) acrylate.

[4] A cured film formed from the radiation sensitive composition according to any one of [1] to [3].

[5] An insulating film for a display element formed from the cured film according to the above [4].

[6] A spacer for a display element formed from the cured film according to [4].

[7] A color filter for a display element formed of the cured film according to [4] above.

[8] A liquid crystal display element comprising the insulating film for a display element according to [5] above.

[9] A liquid crystal display element comprising the display element spacer according to [6].

[10] A liquid crystal display element comprising the color filter for a display element according to [7].

[11] A method for manufacturing an insulating film for a display element, comprising at least the following steps (a) to (d).

(A) a step of forming a film of the radiation sensitive composition described in any one of the above [1] to [3] on a substrate

(B) a step of exposing at least a part of the film to radiation

(C) Step of developing the film after exposure

(D) a step of heating the film after development

[12] A method for producing a spacer for a display element, comprising at least the following steps (a) to (d).

(A) a step of forming a film of the radiation sensitive composition described in any one of the above [1] to [3] on a substrate

(B) a step of exposing at least a part of the film to radiation

(C) Step of developing the film after exposure

(D) a step of heating the film after development

[13] A method of manufacturing a color filter for a display element, comprising at least the following steps (a) to (d).

(A) a step of forming a film of the radiation sensitive composition described in any one of the above [1] to [3] on a substrate

(B) a step of exposing at least a part of the film to radiation

(C) Step of developing the film after exposure

(D) a step of heating the film after development

[14] A coloring composition comprising the copolymer [A], the polymer [B] polymerizable unsaturated compound, the [C] compound, and the solvent and a colorant according to any one of [1] to [3] .

The radiation sensitive composition of the present invention can secure an insulating film, a spacer, and a color filter excellent in focus margin, reworkability, and the like.

1 is a schematic cross-sectional view showing the kind of a cross-sectional shape of a spacer observed with a scanning electron microscope.

(Mode for carrying out the invention)

Each component of the radiation sensitive composition of the present invention will be described in detail below.

- [A] Copolymer -

The component [A] in the radiation sensitive composition of the present invention fulfills a role of facilitating formation of a predetermined pattern which does not generate scum at the time of development. The component (A) in the radiation-sensitive composition of the present invention is preferably a copolymer comprising (a1) a structural unit having an unsaturated carboxylic acid and / or an unsaturated carbonic anhydride (hereinafter collectively referred to as " (Hereinafter referred to as a " compound (a3) ") (hereinafter referred to as a " compound (a2) ") having an epoxy group-containing unsaturated compound Referred to as " [A] copolymer ").

Examples of the compound (a1) include acrylic acid, methacrylic acid, crotonic acid, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), hexahydrophthalic acid mono Monocarboxylic acids such as acryloyloxyethyl (methacryloyloxyethyl) acrylate and mono (2-methacryloyloxyethyl) hexahydrophthalate; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And the like.

Of these compounds (a1), acrylic acid, methacrylic acid, maleic anhydride and the like are preferred because of their ease of copolymerization reactivity and availability.

The above-mentioned compound (a1) may be used alone or in combination of two or more.

In the [A] copolymer, the content of the constituent unit derived from the compound (a1) is preferably from 5 to 50% by weight, more preferably from 10 to 40% by weight. In this case, if the content of the constituent unit is less than 5% by weight, the resolution and sensitivity of the resulting radiation sensitive composition tends to decrease. On the other hand, if it exceeds 50% by weight, the storage stability of the radiation sensitive composition There is a concern.

Examples of the compound (a2) include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 6,7-epoxyheptyl Cyclohexylmethyl (meth) acrylate,? -Ethylglycidyl (meth) acrylate, propylglycidyl (meth) acrylate, 3,4-epoxycyclohexyl (Meth) acrylate and oxetane (meth) acrylate, ethers such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether, And the like.

Among these compounds (a2), glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (Meth) acrylate, and oxetane (meth) acrylate are preferred from the viewpoint of copolymerization reactivity and strength of the resultant spacer.

The compound (a2) may be used alone or in combination of two or more.

In the [A] copolymer, the content of the structural unit derived from the compound (a2) is preferably 10 to 70% by weight, more preferably 20 to 60% by weight. In this case, if the content of the constituent unit is less than 10% by weight, the heat resistance and chemical resistance of the obtained insulating film, spacer and color filter tend to decrease. On the other hand, if the content exceeds 70% by weight, the storage stability of the radiation- There is a tendency to decrease.

As the compound (a3), for example, styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, o-hydroxystyrene, m- p-hydroxystyrene, and the like.

Of these compounds (a3), styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and the like are preferable from the viewpoint of copolymerization reactivity.

The above-mentioned compound (a3) may be used alone or in combination of two or more.

In the [A] copolymer, the content of the structural unit derived from the compound (a3) is preferably from 10 to 80% by weight, more preferably from 20 to 60% by weight. In this case, if the content of the constituent unit is less than 10% by weight, heat resistance of the obtained insulating film, spacer and color filter may be lowered. On the other hand, if the content exceeds 80% by weight, .

In addition, the compound (a4) may be included. As the compound (a4), for example, there may be mentioned methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylates such as isopropyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate and t- hexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane-8-yl (meth) acrylate (hereinafter referred to as D "a" tricyclo [5.2.1.0 ^2,6] decane-8-one " Alicyclic ester (meth) acrylates such as 2-dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate and tetrahydrofuryl (meth) (Meth) acrylate, benzyl (meth) acrylate and the like. And the like.

Further, dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) Methacrylate, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3- But are not limited to, butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N- benzylmaleimide, N-succinimidyl-3-maleimide benzoate, 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (9-acridinyl) maleimide and the like.

The compound (a4) may be used alone or in combination of two or more.

In the [A] copolymer, the content of the constituent unit derived from the compound (a4) is preferably 0 to 80% by weight, more preferably 20 to 60% by weight. In this case, if the content of the constituent unit exceeds 80% by weight, the resolution of the radiation sensitive composition may deteriorate.

The polystyrene reduced weight average molecular weight (hereinafter referred to as " Mw ") of the copolymer [A] by gel permeation chromatography (GPC) is usually 2 × 10 ^{3 to} 5 × 10 ⁵ , preferably 5 × 10 ³ ~ 1 × 10 ⁵ . In this case, when the Mw of the [A] copolymer is less than 2 x 10 ³ , the compressive strength and heat resistance of the obtained spacer tends to decrease. On the other hand, when the Mw exceeds 5 x 10 ⁵ , the developability tends to decrease.

In the present invention, the [A] copolymers may be used alone or in combination of two or more.

The [A] copolymer can be produced by radical polymerization of the compound (a1), the compound (a2) and the compound (a3) in a solvent, for example, in the presence of a polymerization initiator. Examples of the solvent used in the production of the copolymer [A] include alcohols such as methanol, ethanol, n-propanol, i-propanol, benzyl alcohol, 2-phenylethanol and 3-phenyl-1-propanol;

Ethers such as tetrahydrofuran and dioxane;

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol mono-n-propyl ether;

Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and ethylene glycol mono-n-propyl ether acetate;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate and diethylene glycol monoethyl ether acetate;

Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate and ethylene glycol mono-n-propyl ether propionate;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and diethylene glycol dimethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol mono-n-propyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol mono-n-propyl ether acetate;

Propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate and propylene glycol mono-n-propyl ether propionate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone;

Propyl methacrylate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n- Propyl methoxypropionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, 2-n-butoxypropionic acid methyl, n-propyl, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, Alkoxypropionic acid alkyls such as n-propyl butoxypropionate;

Propyl acetate, methyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxypropionate, methyl 2-hydroxypropionate, Methyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, ethoxyacetate, ethoxyacetate, other esters such as methyl n-propoxyacetate, ethyl n-propoxyacetate, methyl n-butoxyacetate and ethyl n-butoxyacetate

And the like.

Of these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkoxypropionic acid alkyls and the like are preferable.

These solvents may be used alone or in combination of two or more.

As the polymerization initiator used in the production of the copolymer [A], those known as radical polymerization initiators can be used, and for example, 2,2'-azobisisobutyronitrile, 2,2'- Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4'- azobis Azo compounds such as dimethyl-2,2'-azobis (2-methylpropionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide , Organic peroxides such as lauroyl peroxide, t-butyl peroxypivalate, and 1,1'-bis (t-butylperoxy) cyclohexane, hydrogen peroxide and the like. When a peroxide is used as the radical polymerization initiator, a redox initiator may be used in combination with a reducing agent.

These radical polymerization initiators may be used alone or in combination of two or more.

- [B] Polymerizable unsaturated compound -

As the polymerizable unsaturated compound in the radiation sensitive composition of the present invention, heat resistance, sensitivity, etc. of the pattern obtained from the radiation sensitive composition can be improved.

As the polymerizable unsaturated compound in the radiation sensitive composition of the present invention, acrylate esters and methacrylate esters having two or more functional groups (hereinafter collectively referred to as "(meth) acrylic acid esters") are preferable.

Examples of the bifunctional (meth) acrylate esters include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1 , 9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, Bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, and the like.

Examples of commercial products of bifunctional (meth) acrylic acid esters include Aronix M-210, M-240, M-6200 (manufactured by TOAGOSEI CO., LTD.), KAYARAD HDDA, KAYARAD HX -220, the R-604, the UX-2201, the UX-2301, the UX-3204, the UX-3301, the UX-4101, the UX-6101, the UX-7101, the UX- -2100, MU-4001 (manufactured by Nippon Kayaku Co., Ltd.), Viscot 260, 312 and 335 HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the (meth) acrylic esters having three or more functional groups include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacryl Acrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) acrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, (2-methacryloyloxyethyl) phosphate, a compound having two or more isocyanate groups and having a linear alkylene group and an alicyclic structure as a (meth) acrylic acid ester having 9 or more functional groups and , Having at least one hydroxyl group in the molecule, and three, four or five acryloyloxy groups and And / or a methacryloyloxy group, and the like can be given.

Examples of commercial products of the trifunctional or more (meth) acrylic acid esters include Aronix M-309, M-400, M-402, M-405, M- M-9060, M-8050, M-8060, M-8100, M-8530, M-8560, M-9050, ARONIX TO-1450 , KOHARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-40, copper DPCA-60, copper DPCA-120, 3510 (manufactured by Nippon Kayaku Co., Ltd.), Viscot 295, 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (manufactured by Osaka Organic Chemical Industry Co., New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned as a commercially available product containing the compound.

In the present invention, the polymerizable unsaturated compounds may be used alone or in admixture of two or more.

In the radiation-sensitive composition of the present invention, the amount of the polymerizable unsaturated compound to be used is preferably 30 to 200 parts by weight, more preferably 30 to 150 parts by weight, particularly preferably 30 to 100 parts by weight based on 100 parts by weight of the [A] Is from 40 to 100 parts by weight. In this case, if the amount of the polymerizable unsaturated compound is less than 30 parts by weight, the resulting insulating film tends to have lower heat resistance and chemical resistance, less spacer film and lower strength, and lower heat resistance and chemical resistance of the color filter On the other hand, if it exceeds 200 parts by weight, the resolution of the radiation sensitive composition may decrease.

- [C] Radiation-induced Polymerization Initiator -

The radiation-sensitive polymerization initiator in the radiation-sensitive composition of the present invention may be a compound represented by the following general formula (1) (hereinafter referred to as "compound (1)") or a compound represented by the following general formula (2 , &Quot; compound (2) ").

(In the formula (1), R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a heterocyclic group, or a (meth) , And n represents 0 to 1.

In the formula (2), R ₄ represents a hydrogen atom, a halogen atom, a nitro group, a thiophenecarboxyaldehyde group or a tolualdehyde group. R ₅ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms. R ₆ represents an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a heterocyclic ring or a (meth) acryloyl group.

_{R 1, R 2, R 3} , R 5, R 6 are, for example, as a straight-chain alkyl group on the branches of 1 to 10 carbon atoms, e.g., methyl, ethyl, n- propyl, i- propyl butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, , an n-undecyl group, and an n-dodecyl group. The cyclic hydrocarbon group having 1 to 10 carbon atoms includes, for example, an isobornyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a benzyl group.

Examples of the halogen atom of R ₁ to R ₆ include a fluorine atom, a chlorine atom and a bromine atom.

Specific examples of the preferable compound (1) in the present invention include the following compounds.

(C-1-1)

(C-1-2)

(C-1-3)

(C-1-4)

(C-1-5)

(C-1-6)

(C-1-7)

Among these compounds (1), (C-1-1), (C-1-2) and (C-1-7) are more preferable.

The compound (1) is a component capable of forming an insulating film, a spacer, and a color filter which are excellent in solubility in a solvent, do not generate foreign matter such as undissolved products and precipitates, and have excellent focus margin.

In the present invention, the compounds (1) may be used alone or in combination of two or more.

Specific examples of the preferable compound (2) in the present invention include the following compounds.

(C-2-1)

(C-2-2)

(C-2-3)

(C-2-4)

(C-2-5)

(C-2-6)

Of these compounds (2), (C-2-1) and (C-2-2) are more preferable.

The compound (2) is a component capable of forming an insulating film, a spacer, and a color filter which are excellent in solubility in a solvent, do not generate foreign matter such as undissolved products and precipitates, and have excellent focus margin.

In the present invention, the compounds (2) may be used alone or in combination of two or more.

The amount of the compound (1) and the compound (2) to be used in the radiation-sensitive composition of the present invention is preferably 3 to 50 parts by weight, more preferably 3 to 30 parts by weight, per 100 parts by weight of the [A] By weight, particularly preferably 3 to 20 parts by weight. In this case, when the amount of the compound (1) and the compound (2) is less than 3 parts by weight, the residual film tends to decrease. On the other hand, if it exceeds 50 parts by weight, the solubility of the unexposed portion in an alkali developing solution tends to decrease.

In the radiation-sensitive composition of the present invention, other radiation-sensitive polymerization initiators and sensitizers may be used together with the compound (1) or the compound (2).

- Optional additives -

The radiation sensitive composition of the present invention may optionally contain optional additives other than the above components such as a surfactant, an adhesion agent, a storage stabilizer, a heat resistance improving agent, a colorant, a dispersant, etc. Can be blended.

(Surfactants)

The above-mentioned surfactant is a component blended to improve the coating property, and a fluorine-based surfactant and a silicon-based surfactant are preferable.

As the fluorine-based surfactant, a compound having a fluoroalkyl and / or fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable, and examples thereof include 1,1,2,2-tetrafluoro-n Octyl (1, 1, 2, 2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (1,2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di , 2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, 3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, perfluoro-n-dodecane sulfonic acid Sodium fluoride, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarbonate, fluoroalkylpoly Perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyalkanes, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyethers, perfluoroalkylpolyoxyalkyl ethers, Fluorine-based alkyl esters and the like.

Examples of commercially available products of the fluorine-based surfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Copper F172, Copper F173, Copper F178, Copper F183, Copper F191, Copper F471 , FC-431, FC-431 (manufactured by Sumitomo 3M Co., Ltd.), Surflon (registered trademark of Sumitomo 3M Co., Ltd.) S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103 and SC-104 (Manufactured by Asahi Glass Co., Ltd.), F-EF301, EF303 and EF352 (manufactured by Shin-Akitakasei Co., Ltd.), Fotogent FT-100 and FT- 110, FT-140A, FT-150, FT-250, FT-251, FT-300, FT-310, FT-400S, FTX-218 and FTX-251 Manufactured by NEOS), and the like.

Examples of the silicone surfactants include Toray silicon DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- (Manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 (Manufactured by GE Toshiba Silicone Co., Ltd.), and the like.

Examples of the surfactant other than the above surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether , Polyoxyethylene aryl ethers such as polyoxyethylene n-nonylphenyl ether and the like, polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and nonionic surfactants such as commercially available products , KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57 and No. 95 (manufactured by Kyoeisha Kagaku Co., Ltd.), and the like.

These surfactants may be used alone or in combination of two or more.

The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the [A] copolymer. In this case, when the blending amount of the surfactant is more than 5 parts by weight, the film tends to become rough during coating.

(Adhesive agent)

The adhesive agent is a component to be blended to further improve adhesion with a substrate.

As such adhesives, a functional silane coupling agent is preferable, and examples thereof include silane coupling agents having reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group and epoxy group. More specifically, , Trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanate propyltriethoxysilane,? -Glycidoxypropyltrimethoxy Silane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

These adhesive agents may be used alone or in admixture of two or more.

The blending amount of the adhesive agent is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the [A] copolymer. In this case, when the blending amount of the adhesive agent exceeds 20 parts by weight, development residue tends to be easily generated.

(Storage stabilizer)

Examples of the storage stabilizer include sulfur, a quinone, a hydroquinone, a polyoxy compound, an amine, and a nitrino nitro compound. Examples of the storage stabilizer include 4-methoxyphenol, N-nitroso- - phenylhydroxylamine aluminum and the like.

The amount of the preservative stabilizer to be used is preferably 3.0 parts by weight or less, more preferably 1.5 parts by weight or less, based on 100 parts by weight of the [A] copolymer. In this case, if the amount of the preservative stabilizer used exceeds 3.0 parts by weight, the sensitivity may be lowered and the shape of the spacer may be damaged.

(Heat resistance improver)

Examples of the heat resistance improving agent include an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, a compound having two or more epoxy groups, and the like.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) N, N, N, N-tetra (n-propoxymethyl) glycoluril, N, N, Butoxymethyl) glycoluril, N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like.

Among these N- (alkoxymethyl) glycoluril compounds, N, N, N, N-tetra (methoxymethyl) glycoluril is preferable.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, Melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, , N, N, N, N, N-hexa (t-butoxymethyl) melamine and N, N, N, N, N, N-hexa (t-butoxymethyl) melamine.

Among these N- (alkoxymethyl) melamine compounds, N, N, N, N, N, N-hexa (methoxymethyl) melamine is preferable. Examples of commercial products thereof include NIKARAK N-2702, -30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol Diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether , Hydrogenated bisphenol A diglycidyl ether, and bisphenol A diglycidyl ether.

Examples of commercial products of compounds having two or more epoxy groups include Epolite 40E, Copper 100E, Copper 200E, Copper 70P, Copper 200P, Copper 400P, Copper 1500NP, Copper 1600, Copper 80MF, Copper 100MF, Copper 3002 , 4000 (manufactured by Kyoeisha Chemical Co., Ltd.), and the like.

These heat resistance improving agents may be used alone or in combination of two or more.

The radiation sensitive composition of the present invention is preferably provided for use as a composition solution dissolved in a suitable solvent.

As the above-mentioned solvent, those having the appropriate volatility can be used without dissolving each component constituting the radiation-sensitive composition uniformly and reacting with each component.

As such a solvent, for example, the same solvents as those exemplified for the polymerization for producing the [A] copolymer can be mentioned.

From the viewpoints of the solubility of each component, the reactivity with each component, and the ease of film formation, among these solvents, alcohols, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, diethylene glycol alkyl ethers , Propylene glycol monoalkyl ether acetates and alkoxypropionic acid alkyls, and the like. Particularly preferred are benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, diethylene glycol mono Ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and the like are preferable.

These solvents may be used alone or in combination of two or more.

In the present invention, a high boiling point solvent may be used in combination with the above-mentioned solvent.

Examples of the high-boiling solvent include N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, benzylethylether, dihexylether, acetonyl acetone, iso Butanediol, dihydroterephosphoric acid, dihydroterephinyl acetate, terpolone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, 2,2,4-trimethyl- Phenol, limonene, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate and the like.

These high boiling point solvents may be used alone or in combination of two or more.

In addition, the composition solution prepared as described above may be filtered by using a millipore filter having a pore diameter of about 0.5 mu m to provide the solution for use.

The radiation sensitive composition of the present invention may contain a coloring agent. Thus, for example, a coloring and radiation-sensitive composition for forming a colored layer can be used. Here, the " colored layer " means each color pixel used in a color filter, a black matrix used in a liquid crystal display element, a black spacer, and the like. The coloring agent is not particularly limited as long as it has coloring property, and color or material can be appropriately selected depending on the application of the radiation-sensitive composition. When the radiation sensitive composition of the present invention is used for forming a coloring layer of a color filter, at least one coloring agent selected from a pigment and a dye is preferable in view of high color purity, brightness, contrast and the like required for the color filter.

Specific examples of the organic pigments may include CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment (CI Pigment Red 166, Red 242, CI Pigment Red 254, CI Pigment Red 264, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Blue 15: 6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 38 , CI Pigment Violet 23, and the like. Preferable specific examples of the inorganic pigments include carbon black, titanium black and the like.

As a pigment, a rake pigment is also preferable, and specifically, a rake of a triarylmethane dye or a zanthene dye with an isopoly acid or a heteropoly acid can be mentioned. The triarylmethane lake pigment is disclosed, for example, in JP-A-2007-186043. Zanthane lake pigments are disclosed in, for example, Japanese Laid-Open Patent Publication No. 2010-191304.

As the dyes, there are preferably used dyestuff dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes and azo dyes. More specifically, Japanese Laid-Open Patent Publication No. 2010-32999, Japanese Laid-Open Patent Publication No. 2010-254964, Japanese Laid-Open Patent Publication No. 2011-138094, International Laid-Open Pamphlet No. 10/123071, Japanese Laid-Open Patent Publication No. 2011-116803, Organic dyes described in Japanese Patent Application Laid-Open No. 11-17995, Japanese Laid-Open Patent Publication No. 2011-133844, Japanese Laid-Open Patent Publication No. 2011-174987, and the like.

In the present invention, the pigment and the dye may be used alone or in combination of two or more.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. The pigment may be used by modifying its particle surface with a resin, if desired. Further, the organic pigment can be used by finely grinding primary particles by so-called salt milling. As a method of the salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. 08-179111 can be adopted.

The content of the colorant is usually from 5 to 70% by mass, preferably from 5 to 60% by mass, in the solid matter of the radiation sensitive composition, from the viewpoint of forming a pixel having a high luminance and excellent color purity or a black matrix having excellent light- %to be.

When a pigment is used as a colorant in the present invention, it can be used together with a dispersant and a dispersion aid if desired. As the dispersing agent, for example, a suitable dispersing agent such as cationic, anionic, and nonionic ones can be used, but a polymer dispersing agent is preferable. Specific examples thereof include acrylic copolymers, polyurethanes, polyesters, polyethyleneimines, polyallylamines, and the like.

Dispersing agents such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 and BYK-LPN21324 (manufactured by BYK) are commercially available as the acrylic copolymer. Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 and Disperbyk-2164 (manufactured by BYK), Solpres 76500 (Manufactured by Ajinomoto Pine Techno Co., Ltd.) as polyethylene imine, Solsperse 24000 (manufactured by Rubrizol Corporation) as a polyethyleneimine, and Ajisper PB821, Ajisper PB822 and Ajisper PB880 (manufactured by Ajinomoto Fine Techno Co., Ltd.) as polyesters. As the acrylic copolymer, copolymers disclosed in Japanese Unexamined Patent Application Publication No. 2011-232735, Japanese Unexamined Patent Application Publication No. 2011-237769 and Japanese Unexamined Patent Publication No. 2012-32767 can be suitably used. The content of the dispersant can be appropriately determined within a range that does not impair the object of the present invention.

Examples of the dispersion aid include pigment derivatives, and specific examples thereof include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The content of the dispersing aid can be suitably determined within a range not hindering the object of the present invention.

≪ Method of forming insulating film, spacer, color filter >

Next, a method of forming each color pixel and black matrix constituting the insulating film, the spacer, and the color filter of the present invention using the radiation sensitive composition of the present invention will be described.

The formation of the insulating film, spacer, pixel of each color, and black matrix of the present invention includes at least the following processes (A) to (D).

(A) A step of forming a film of the radiation sensitive composition of the present invention on a substrate.

(B) A step of exposing radiation to at least a part of the coating film.

(C) a step of developing the film after exposure.

(D) a step of heating the film after development.

Hereinafter, each of these steps will be described in sequence.

- (A) Process -

After applying the composition solution of the radiation sensitive composition of the present invention onto one side of the transparent substrate, the coated surface is heated (prebaked) to form a film.

Examples of the transparent substrate used for forming the insulating film, the spacer, the pixel for each color, and the black matrix include a glass substrate and a resin substrate, and more specifically, a glass substrate such as soda lime glass or alkali- ; And resin substrates made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide.

As the transparent conductive film provided on one surface of the transparent substrate, an ITO film made of a NESA film (registered by the US PPG company) and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) .

As a coating method of the composition solution, a suitable method such as a spray coating method, a roll coating method, a rotation coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet coating method, Particularly, a spin coating method or a slit die coating method is preferable.

The conditions for prebaking vary depending on the kind of each component, blending ratio and the like, but are usually about 1 to 15 minutes at 70 to 120 캜.

- (B) Process -

Then, at least a portion of the formed coating is exposed to radiation. In this case, when a part of the coating film is exposed, the film is usually exposed through a photomask having a predetermined pattern.

As the radiation to be used, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. However, radiation having a wavelength in the range of 190 to 450 nm is preferable and radiation containing ultraviolet light having a wavelength of 365 nm is preferable Do.

The exposure dose is a value measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm of the exposed radiation, and is usually 100 to 10,000 J / m2, preferably 1,500 to 3,000 J / M < 2 >.

- (C) Process -

Subsequently, the exposed film is developed to remove unnecessary portions to form a predetermined pattern.

Examples of the developer used in the development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; aliphatic primary amines such as ethylamine and n-propylamine; Aliphatic secondary amines such as amine, di-n-propylamine and the like; aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; aliphatic tertiary amines such as pyrrole, piperidine, Alicyclic tertiary amines such as N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] , Aromatic tertiary amines such as collidine, lutidine and quinoline, alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Or an aqueous solution of an alkaline compound It can be used.

Further, a water-soluble organic solvent such as methanol and ethanol and / or a surfactant may be added in an appropriate amount to the aqueous solution of the alkaline compound.

As the developing method, any of a puddle method, a dipping method and a shower method may be used, and the developing time is usually about 10 to 180 seconds at normal temperature.

After development, for example, water washing is performed for 30 to 90 seconds, and then air is blown with, for example, compressed air or compressed nitrogen to form a desired pattern.

- (d) Process -

Subsequently, the obtained pattern is heated at a predetermined temperature, for example, 100 to 160 占 폚 for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 30 to 30 minutes in an oven by a heating apparatus such as a hot plate or an oven (Post baking) for 180 minutes to obtain a predetermined insulating film and a spacer.

The insulating film, the spacer, the color pixel, and the black matrix can not exhibit sufficient performance unless the heat treatment is performed at a temperature of about 180 to 200 deg. C or higher in the conventional radiation sensitive composition used for forming the insulating film and the spacer. The radiation sensitive composition of the present invention can be heated at a lower temperature than conventional, and as a result, an insulating film having excellent reworkability can be obtained without causing yellowing or deformation of the resin substrate. In addition, it is possible to provide a spacer excellent in performance of reworkability, sectional shape, and rubbing resistance. Further, each color pixel and black matrix having excellent reworkability can be obtained.

As a method for forming the coloring layer constituting the color filter, first, the following method can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate so as to partition a portion where a pixel is formed, if necessary. Subsequently, a liquid composition of the radiation sensitive curable composition of the present invention containing, for example, a red coloring agent is applied on the substrate, and then the substrate is prebaked to evaporate the solvent to form a coating film. Subsequently, this coating film is exposed through a photomask and then developed with an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which red pixel patterns are arranged in a predetermined arrangement is formed.

Subsequently, the respective radiation-sensitive curable compositions were applied, pre-baked, exposed, developed, and post-baked in the same manner as above using each of the green or blue radiation sensitive curable compositions to form a green pixel array and a blue Pixel arrays are sequentially formed on the same substrate. Thus, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

<Display element>

The display element of the present invention comprises the insulating film, spacer, and color filter layer of the present invention formed as described above.

The structure of the display element is not particularly limited. For example, a structure in which a color filter, an insulating film and a spacer of the present invention are formed on a transparent substrate, two alignment films disposed through the liquid crystal layer, an opposing transparent electrode, A substrate, and the like. If necessary, a protective film may be formed on the polarizing plate or the color filter layer.

Further, a TN-TFT type liquid crystal display device can also be formed by forming a color filter layer, an insulating film and a spacer of the present invention on a transparent substrate, and opposing the array of thin film transistors (TFT) through an alignment film and a liquid crystal layer. In this case as well, a protective film can be formed on the polarizing plate or the color filter layer, if necessary.

(Example)

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following description of examples and the like, &quot; part &quot; means &quot; part by mass &quot; unless otherwise stated.

[Weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (Mw / Mn)] [

Mw and Mn of the resin were measured by gel permeation chromatography (GPC) under the following analytical conditions using a GPC column (G2000HXL 2, G3000HXL 1, G4000HXL 1) from Toso Co., The dispersion degree (Mw / Mn) was calculated from the measurement results of Mw and Mn.

(Analysis condition)

Elution solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Column temperature: 40 DEG C

Detector: differential refractometer

Standard material: monodisperse polystyrene

<Synthesis of alkali-soluble resin>

[Synthesis Example 1]

15 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of methyl 3-methoxypropionate were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Subsequently, 30 parts of methacrylic acid, 30 parts of 3,4-epoxycyclohexylmethyl methacrylate, and 40 parts of styrene were added. After nitrogen displacement, stirring was begun slowly. The temperature of the solution was raised to 70 캜, and this temperature was maintained for 5 hours to obtain a solution containing the alkali-soluble resin (A-1). The solid concentration of the solution was 35.2 mass%, the Mw of the resin (A-1) was 8,000, and the Mw / Mn was 2.1.

[Synthesis Example 2]

A solution containing the alkali-soluble resin (A-2) was obtained in the same manner as in Synthesis Example 1 except that each component of the type and compounding amount shown in Table 1 below was used. The solid concentration of the solution was 35.2 mass%, the Mw of the resin (A-2) was 8,000, and the Mw / Mn was 2.0.

[Synthesis Example 3]

A solution containing the alkali-soluble resin (A-3) was obtained in the same manner as in Synthesis Example 1 except that each component of the type and compounding amount shown in Table 1 below was used. The solid content concentration of the solution was 35.2 mass%, the Mw of the resin (A-3) was 8,000, and the Mw / Mn was 2.0.

[Synthesis Example 4]

A solution containing the alkali-soluble resin (A-4) was obtained in the same manner as in Synthesis Example 1 except that the components shown in the following Table 1 and the respective amounts were used. The solid concentration of the solution was 35.2% by mass, the Mw of the resin (A-4) was 12,000, and the Mw / Mn was 2.5.

Alkali-soluble resin A-1 A-2 A-3 A-4 Methacrylic acid 30 30 30 30 3,4-epoxycyclohexylmethyl methacrylate 30 0 15 35 Styrene 40 40 40 0 Glycidyl methacrylate 0 30 15 35 Solid content concentration (% by mass) 35.2 35.2 35.2 35.2 Mw 8000 8000 8000 12000 Mw / Mn 2.1 2 2 2.5

<Preparation of Curable Resin Composition>

[Example 1]

5 parts (C) of a radiation-sensitive polymerization initiator (C-1-1) was added to a solution containing the resin (A-1) , 50 parts of a polymerizable unsaturated compound (B) (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.), (D) 50 parts of a pressure sensitive adhesive (methacryloxypropyl 3 parts of trimethoxysilane (XIAMETER (R) OFS-6030 SILANE from Toray Dow Corning), (E) 3 parts of ultraviolet absorber (2,2 ', 4,4'-tetrahydroxybenzophenone ), And the resulting mixture was dissolved in a mixed solvent of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate (mass ratio 50:50) so as to have a solid content concentration of 30% by mass. Thereafter, a membrane filter To obtain a resin composition (S-1).

[Examples 2 to 17 and Comparative Examples 1 to 3]

(S-2) to (S-17) and (CS-1) to (CS-3) were obtained in the same manner as in Example 1 except that the components shown in Table 2 were used, .

The meanings of the symbols in the following Table 2 are as follows.

The resin (A) and other resins

A-1 to A-4: Resins synthesized in Synthesis Examples 1 to 4

Radiation-sensitive polymerization initiator (C):

C-1-1: A compound represented by the formula (C-1-1)

C-1-2: A compound represented by the formula (C-1-2)

C-1-3: A compound represented by the formula (C-1-3)

C-1-4: A compound represented by the formula (C-1-4)

C-1-5: Compound represented by the formula (C-1-5)

C-1-6: A compound represented by the above formula (C-1-6)

C-1-7: A compound represented by the above formula (C-1-7)

C-2-1: A compound represented by the formula (C-2-1)

C-2-2: A compound represented by the formula (C-2-2)

C-2-3: Compound represented by the formula (C-2-3)

C-2-4: A compound represented by the above formula (C-2-4)

C-2-5: A compound represented by the above formula (C-2-5)

C-2-6: A compound represented by the formula (C-2-6)

C-3: 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] ("Irgacure OXE01"

C-4: Ethanol-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) ("Irgacure OXE02" )

<Evaluation>

An insulating film was formed from the resin compositions obtained in Examples and Comparative Examples, and the focus margin, the workability, the sensitivity and the resolution were evaluated according to the following method. The evaluation results are shown in Table 2 below.

[Focus margin]

An insulating film having a through-hole was formed in the same manner as in the evaluation of the radiation sensitivity described below except that the exposure amount was changed to 200 J / m &lt; 2 &gt;, and the margin of the focus deviation, in which the rate of change of the through- Observed. The focus margin was evaluated according to the following criteria.

(Evaluation standard)

A: The focus margin is 50 占 퐉 or more

B: a focus margin of 30 占 퐉 or more and less than 50 占 퐉

C: The focus margin is 0 탆 or more and less than 30 탆

[Re-workability]

An insulating film was formed in the same manner as in the evaluation of the radiation sensitivity described below except that the exposure amount was changed to 200 J / m 2, and the film was immersed in N-300 (manufactured by Nagase Chemtech) at 75 ° C for an arbitrary time, We evaluated the castle.

(Evaluation standard)

A: Total peeling within 10 minutes of immersion time

B: Total peeling within 10 minutes to 30 minutes of immersion time

C: Complete peeling at a dipping time of 30 minutes or longer

[Sensitivity]

The resin compositions obtained in Examples and Comparative Examples were applied to a glass substrate ("Corning 7059" by Corning Inc.) using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 4.0 μm did.

Subsequently, the exposure amount was changed using an exposure machine ("MPA-600FA" manufactured by Canon Inc.: using an ultra-high pressure mercury lamp, lens aperture ratio = 0.10, sigma = 0.5) to obtain a plurality of rectangular light shielding portions (5 mu m x 5 mu m) And the coating film was exposed through a pattern mask. Subsequently, development processing was carried out at 25 占 폚 by a puddle method using a tetramethylammonium hydroxide aqueous solution (developing solution) at a concentration of 2.38 mass%. The development processing time was 100 seconds. After the developing treatment, the coating film was washed with water with ultra-pure water for 1 minute and dried to form a pattern on the glass substrate. This glass substrate was heated in a clean oven at 230 DEG C for 30 minutes to obtain an insulating film.

The exposure amount at which the residual film ratio (the ratio at which the pattern-like thin film properly remains) represented by the following formula was 85% or more with respect to the film thickness of the insulating film was determined as the sensitivity, and the sensitivity was evaluated according to the following criteria.

Remaining film ratio (%) = (film thickness after development / film thickness before development) x 100

(Evaluation standard)

A: Less than 200 J / m

B: 200 J / m 2 or more and less than 400 J / m 2

C: over 400J / ㎡

[Resolution]

An insulating film having a through hole was formed in the same manner as in the above evaluation of radiation sensitivity except that the exposure dose was changed to 200 J / m &lt; 2 &gt;, and the minimum diameter of the through hole of the insulating film was observed with an optical microscope. The resolution was evaluated according to the following criteria.

(Evaluation standard)

A: The minimum diameter of the through hole is 5 占 퐉 or more

B: Minimum diameter of the through-hole is 3 탆 or more and less than 5 탆

C: Minimum diameter of through hole is 1 탆 or more and less than 3 탆

The insulating films of Comparative Examples 1 and 2 had deteriorated focus margin and reworkability. Therefore, the insulating film in the present invention can be suitably used, for example, as a planarizing film or an interlayer insulating film of a display element.

[Evaluation of Spacer]

[Example 18]

20 parts (C) of a radiation-sensitive polymerization initiator (C-1-1) was added to a solution containing the resin (A-1) in an amount of 100 parts (solid content) , 100 parts of a polymerizable unsaturated compound (B) (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate ("KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.), (D) 100 parts of a pressure sensitive adhesive (methacryloxypropyl (F) surfactant (Fotogen FTX-218) 0.5 part, (E) 5 parts of ultraviolet absorber (2,2 ', 4,4'-tetrahydroxybenzophenone And 0.5 parts of antioxidant (G) were mixed, and the obtained mixture was dissolved in a mixed solvent of methyl 3-methoxypropionate and propylene glycol monomethyl ether acetate (mass ratio 50:50) so that the solid concentration became 30% by mass, And filtered through a membrane filter having a pore size of 0.2 탆 to prepare a resin composition (S-18).

[Examples 19 to 34 and Comparative Examples 4 to 6]

(S-19) to (S-34) and (CS-4) to (CS-6) were obtained in the same manner as in Example 18 except that the components shown in Table 3 were used, .

[Focus margin]

A spacer was formed in the same manner as in the evaluation of the radiation sensitivity described below except that the exposure dose was changed to 1500 J / m &lt; 2 &gt;, and the margin of the focus shift, in which the rate of change of the spacer was 10% or less, was observed with an optical microscope. The focus margin was evaluated according to the following criteria.

(Evaluation standard)

A: The focus margin is 50 占 퐉 or more

B: a focus margin of 30 占 퐉 or more and less than 50 占 퐉

C: The focus margin is 0 탆 or more and less than 30 탆

[Re-workability]

A spacer was formed in the same manner as in the evaluation of the radiation sensitivity described below except that the exposure dose was changed to 1500 J / m 2 and immersed in N-300 (manufactured by Nagase Chemtech Co., Ltd.) at 75 ° C for arbitrary time, We evaluated the castle.

(Evaluation standard)

A: Total peeling within 30 minutes of immersion time

B: Total peeling within 30 minutes to 60 minutes of immersion time

C: Total peeling at immersion time of 60 minutes or more

[Sensitivity]

The resin compositions obtained in Examples and Comparative Examples were applied onto a glass substrate ("Corning 7059" by Corning) using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 6.0 μm did.

Subsequently, the amount of exposure was changed using an exposure apparatus ("MPA-600 FA" manufactured by Canon Inc.: using an ultra-high pressure mercury lamp, lens aperture ratio = 0.10, sigma = 0.5) to obtain a pattern having a plurality of rectangular light- And the coating film was exposed through a mask. Subsequently, the resist film was developed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 DEG C for 60 seconds, and then washed with pure water for 1 minute. Thereafter, post baking was performed in an oven at 150 캜 for 120 minutes to form spacers having a predetermined pattern.

The exposure amount at which the residual film ratio (the ratio at which the pattern-like thin film properly remains) represented by the following formula was 85% or more with respect to the film thickness of the insulating film was determined as the sensitivity, and the sensitivity was evaluated according to the following criteria.

Remaining film ratio (%) = (film thickness after development / film thickness before development) x 100

(Evaluation standard)

A: Less than 1500J / ㎡

B: Less than 2000J / m &lt; 2 &gt;

C: over 2000J / ㎡

[Resolution]

A spacer was formed in the same manner as in the evaluation of the radiation sensitivity except that the exposure dose was changed to 1500 J / m &lt; 2 &gt;, and the minimum diameter of the spacer was observed with an optical microscope. The resolution was evaluated according to the following criteria.

(Evaluation standard)

A: Minimum diameter of spacer is less than 5 탆

B: The minimum diameter of the spacer is 5 탆 or more and less than 10 탆

C: The minimum diameter of the spacer exceeds 10 탆

[Cross-sectional shape of spacer]

Sectional shape of the obtained spacer was observed with a scanning electron microscope and evaluated according to which of A to C shown in Fig. At this time, when the pattern edge has a net taper or vertical shape like A or B, it can be said that the sectional shape is good. On the other hand, as shown in C, when the sensitivity is insufficient, the residual film ratio is low, the sectional dimensions are smaller than those of A and B, and the bottom surface is a flat, semi-convex lens shape, In the case of a reversed taper shape (cross-sectional shape in which the side of the film surface is longer than the side of the substrate), the cross-sectional shape is poor in that the risk of peeling off the pattern at the time of subsequent rubbing becomes very great.

[Rubbing Resistance]

The substrate having the spacer formed thereon was coated with a liquid crystal aligning agent AL3046 (trade name, manufactured by JSR Corporation) by a printing machine for applying a liquid crystal alignment film, and then dried at 180 DEG C for 1 hour to obtain a liquid crystal aligning agent To form a coating film.

Thereafter, the coating film was subjected to a rubbing treatment by a rubbing machine having a roll coated with a polyamide cloth, at a roll speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, whether or not the pattern was shaved off or peeled off was evaluated.

[Evaluation of colored resist]

Preparation of dye solution

Preparation of dye solution Example 1

10 parts by mass of the dye (1) and 90 parts by mass of propylene glycol monomethyl ether were mixed to prepare a dye solution (H1). The dye (1) is as follows.

Preparation of dye solution Examples 2 to 5

Dyeing solutions (H2) to (H6) were prepared in the same manner as in Preparation Example 1 of the dye solution except that the dyes (2) to (6) were used in place of the dye (1). The dyes (2) to (6) are as described below.

Dye (1): A triarylmethane dye, which is an acrylic polymer having repeating units having triarylmethane, obtained according to Synthesis Example 6 of JP-A-2016-505655

Dye (2): Polymer A shown in Table 1 of Japanese Laid-Open Patent Publication No. 2014-194007 (a triarylmethane dye which is a salt-forming compound of an acrylic polymer having a repeating unit having an imide anion and a compound (1) )

Dye (3): The dyestuff dye represented by the following formula (5)

Dye (4): The dyestuff dye represented by the following formula (A2)

Dye (5): The dyestuff dye represented by the following formula (6)

Dye (6): &quot; Polymer F &quot; (an acrylic polymer having a repeating unit having an imide anion and a cyanine dye serving as a conditioning compound of CI Basic Red 12) described in Table 1 of JP-A No. 2014-194007,

Synthesis of dispersant

Dispersant Synthesis Example 1

80 parts by mass of n-butyl acrylate, 60 parts by mass of methyl methacrylate, 20 parts by mass of methacrylic acid, and 20 parts by mass of car lens MOI-BM (manufactured by Showa Denko Kogyo Co., Ltd.) were added to a reaction vessel equipped with a stirrer, a thermometer, Ltd.) and 20 parts by mass of ETERNACOLL OXMA (manufactured by Ube Kyosan Kagaku K.K.) were charged and replaced with nitrogen gas. After heating the reaction vessel to 80 캜, a solution obtained by mixing 14 parts by mass of 2-mercapto-2-methyl-1,3-propanediol with 0.1 part by mass of 2,2'-azobisisobutyronitrile was placed in a reaction vessel And reacted for 10 hours. It was confirmed that 95% was reacted by the measurement of the solid content. Subsequently, 39 parts by mass of 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride (trade name BPAF (manufactured by JFE Chemical Co., Ltd.)), 39 parts by mass of C-1015N (bifunctional polycarbonate polyol, 106 parts by mass of polyol C-1015N (having a hydroxyl value of 112 mgKOH / g, manufactured by Kuraray Co., Ltd.), 33 parts by mass of trimellitic anhydride, 392 parts by mass of cyclohexanone and 1,8-diazabicyclo [5.4 .0] -7-undecene was added, and the mixture was reacted at 100 DEG C for 7 hours. The acid value measurement confirmed that at least 98% of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a dispersant A having an amine value of 0 mg KOH / g, an acid value of 73 mg KOH / g and a weight average molecular weight of 25,000 was obtained.

Dispersant Synthesis Example 2

62.6 parts by mass of 1-dodecanol, 287.4 parts by mass of? -Caprolactone and 0.1 part by mass of monobutyltin (IV) oxide as a catalyst were fed into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a stirrer, After substitution, the mixture was heated and stirred at 120 DEG C for 4 hours. After confirming that 98% of the reaction was carried out by measuring the solid content, 73.3 parts by mass of pyromellitic anhydride was added and the reaction was carried out at 120 ° C for 2 hours. The acid value measurement confirmed that at least 98% of the acid anhydride was half-esterified, and the reaction was terminated. Thus, a dispersant B having an amine value of 0 mg KOH / g and an acid value of 49 mg KOH / g was obtained.

Dispersant Synthesis Example 3

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. The mixture was heated to 80 占 폚, and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 2,2'-azobis (2,4-dimethyl Valeronitrile) (6 parts by mass) was added dropwise over 1 hour, and the temperature was maintained and maintained for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 占 폚 and further stirred for 1 hour to obtain dispersant C (solid content concentration: 40% by mass). The dispersant C had Mw of 12,200 and Mn of 6,500.

Preparation of pigment dispersion

Pigment dispersion Preparation Example 1

12 parts by mass of CI Pigment Blue 15: 6 as a colorant, 12 parts by mass of BYK-LPN21116 (solid content concentration of 40 mass%, amine value of 29 mg KOH / g, acid value of 0 mg KOH / g, manufactured by BYK) 12.5 parts by mass of a solution (solid content concentration of 40% by mass), 12 parts by mass of methoxypropanol as a solvent and 51.5 parts by mass of propylene glycol monomethyl ether acetate were treated with a bead mill to prepare a pigment dispersion (p-1) It was prepared.

Pigment dispersion Preparation Example 2

Pigment Dispersion In the same manner as in Preparation Example 1 except that a mixture of 3.36 parts by mass of Dispersant A and 1.44 parts by mass of Dispersant B was used in place of 12 parts by mass of BYK-LPN21116, and the amount of propylene glycol monomethyl ether acetate was changed from 51.5 parts by mass to 71.2 parts by mass The pigment dispersion (p-2) was prepared in the same manner as in the pigment dispersion preparation example 1 except that the pigment dispersion (p-2) was used.

Pigment dispersion Preparation Example 3

Pigment Dispersion A pigment dispersion (p-3) was prepared in the same manner as in Pigment Dispersion Preparation Example 1, except that CI Pigment Red 254 was used instead of CI Pigment Blue 15: 6 as a colorant in Preparation Example 1 did.

&Lt; Preparation and evaluation of colored composition >

Example 35

(A), 36.2 parts by mass of the resin (A-1) solution as the resin (A), and Aronix M-402 (dipentaerythritol) as the polymerizable unsaturated compound 11.9 parts by mass of a mixture of hexaacrylate and dipentaerythritol pentaacrylate, 11.9 parts by mass of KAYARAD DPCA-40 manufactured by Nippon Kayaku Co., Ltd., 11.9 parts by mass of Aronix TO-1382 manufactured by Toagosei Co., , 4.2 parts by mass of C-1-1 as an initiator, 0.4 parts by mass of 2,2 ', 4,4'-tetrahydroxybenzophenone (BASF) as an ultraviolet absorber, (F) (G): 0.5 parts by mass of 4-methoxyphenol as an antioxidant, and propylene glycol monomethyl ether acetate as a solvent were mixed to obtain a resin composition having a solid content concentration of 16 mass% (S-35) was prepared. In Table 4, the content of each solid content contained in the resin composition (S-35) is expressed as parts by mass.

Examples 36 to 47

Resin compositions (S-36) to (S-47) were prepared in the same manner as in Example 35 except that each component in the kind and the compounding amount shown in the following Table 4 was used.

Comparative Examples 7 to 10

Resin compositions (CS-7) to (CS-10) were prepared in the same manner as in Example 35 except that each component in the kind and amount shown in the following Table 4 was used.

The resin compositions obtained in Examples and Comparative Examples were applied on a glass substrate ("Corning 7059" by Corning Inc.) using a spinner, and then prebaked on a hot plate at 80 ° C for 10 minutes to form a coating film having a thickness of 2.5 μm did.

Subsequently, exposure of the coating film through a pattern mask having a plurality of rectangular light shielding portions (10 占 퐉 edges) was performed using an exposure machine ("MPA-600FA" manufactured by Canon Inc.: using an ultrahigh pressure mercury lamp, lens aperture ratio = 0.10, . Subsequently, the resist film was developed with a 0.04 wt% potassium hydroxide aqueous solution (developing pressure: 1 kgf / cm 2) at 25 캜 for 90 seconds, and then rinsed with pure water for 1 minute. Thereafter, post baking was performed in an oven at 200 DEG C for 30 minutes to form a cured film for evaluation in a predetermined pattern.

[Focus margin]

An insulating film having through holes was formed in the same manner as in the evaluation of the curable resin composition except that the exposure amount was set to 400 J / m &lt; 2 &gt;, and the margin of the focus deviation in which the rate of change of the through- did. The focus margin was evaluated according to the following criteria.

(Evaluation standard)

A: The focus margin is 50 占 퐉 or more

B: a focus margin of 30 占 퐉 or more and less than 50 占 퐉

C: The focus margin is 0 탆 or more and less than 30 탆

[Re-workability]

An insulating film was formed in the same manner as in the evaluation of the curable resin composition except that the exposure amount was changed to 400 J / m 2 and immersed in N-300 (manufactured by Nagase Chemtech Co., Ltd.) at 75 캜 for arbitrary time, .

(Evaluation standard)

A: Total peeling within 10 minutes of immersion time

B: Total peeling within 10 minutes to 30 minutes of immersion time

C: Complete peeling at a dipping time of 30 minutes or longer

[Heat resistance]

The resin compositions obtained in Examples and Comparative Examples were applied to a glass substrate ("Corning 7059" by Corning Inc.) using a spinner and then prebaked on a hot plate at 80 ° C for 10 minutes to obtain a coating film having a film thickness of 2.5 μm .

Subsequently, using a pattern mask having a plurality of rectangular light-shielding portions (10 占 퐉 edges) using an exposure machine ("MPA-600 FA" manufactured by Canon Inc.: using a high-pressure mercury lamp, lens aperture ratio = 0.10, Exposure was performed. Subsequently, the resist film was developed with a 0.04 wt% potassium hydroxide aqueous solution (developing pressure: 1 kgf / cm 2) at 25 캜 for 90 seconds, and then rinsed with pure water for 1 minute. Thereafter, post-baking was performed in an oven at 200 DEG C for 30 minutes to form a dot pattern on the substrate. The chromaticity coordinate value (x, y) and the magnetic pole value (Y) in the C light source, the 2-degree field of view, and the CIE colorimetric system were measured with respect to the obtained dot pattern using a color analyzer (MCPD2000 manufactured by Otsuka Respectively.

Subsequently, after the substrate was further baked at 230 DEG C for 90 minutes, the chromaticity coordinate value (x, y) and the stimulus value (Y) were measured to evaluate the color change before and after further baking, i.e., DELTA E * ab . As a result, a case where the value of DELTA E * ab was less than 3.0 was evaluated as &quot;? &Quot;, a case where the value was 3.0 or more and less than 5.0 was evaluated as &quot; DELTA &quot; The evaluation results are shown in Table 4 below. Further, the smaller the value of DELTA E * ab, the better the heat resistance.

[Solubility]

The resin compositions obtained in Examples and Comparative Examples were applied to a soda glass substrate having a SiO ₂ film on its surface for preventing elution of sodium ions using a spin coater and then prebaked on a hot plate at 90 캜 for 2 minutes To form a coating film having a film thickness of 2.5 mu m.

Subsequently, using a pattern mask having a plurality of rectangular light-shielding portions (10 占 퐉 edges) using an exposure machine ("MPA-600 FA" manufactured by Canon Inc.: using a high-pressure mercury lamp, lens aperture ratio = 0.10, Exposure was performed. Subsequently, the resist film was developed with a 0.04 wt% potassium hydroxide aqueous solution (developing pressure: 1 kgf / cm 2) at 25 캜 for 90 seconds, and then rinsed with pure water for 1 minute. Thereafter, post-baking was performed in an oven at 200 DEG C for 30 minutes to form a dot pattern on the substrate.

The substrate was immersed in propylene glycol monomethyl ether acetate at 80 DEG C for 40 minutes. The chromaticity coordinate value (x, y) and the stimulus value (Y) before and after immersion were measured, and the color change before and after immersion, that is, DELTA E * ab was evaluated. As a result, a case where the value of DELTA E * ab was less than 3.0 was evaluated as &quot;? &Quot;, a case where the value was 3.0 or more and less than 5.0 was evaluated as &quot; DELTA &quot; The evaluation results are shown in Table 4 below. In addition, the smaller the value of DELTA E * ab, the better the solvent resistance.

Claims (14)

[A] (a1) a structural unit having a carboxyl group,
(a2) a structural unit having an epoxy group,
(a3) a structural unit having a styrene derivative compound
, &Lt; / RTI &gt;
[B] a polymerizable unsaturated compound,
[C] a compound represented by the following formula (1) or (2), and
menstruum
&Lt; / RTI &gt;

(In the formula (1), R ₁ , R ₂ and R ₃ each independently represent an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a heterocyclic group, or a (meth) ; N represents 0 to 1;
In the formula (2), R ₄ represents a hydrogen atom, a halogen atom, a nitro group, a thiophenecarboxyaldehyde group or a tolualdehyde group; R ₅ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 10 carbon atoms; R ₆ represents an alkyl group having 1 to 10 carbon atoms or a cyclic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a halogen atom, a heterocyclic ring or a (meth) acryloyl group. The method according to claim 1,
The copolymer of [A]
(a1) 3 to 30 mass% of a structural unit having a carboxyl group,
(a2) 20 to 60% by mass of a structural unit having an epoxy group,
(a3) 10 to 77 mass% of a structural unit having a styrene derivative compound
&Lt; / RTI &gt; The method according to claim 1,
Wherein the structural unit having an epoxy group in the [A] (a2) is at least one selected from the group consisting of glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, And cetane (meth) acrylate. A cured film formed from the radiation sensitive composition according to any one of claims 1 to 3. An insulating film for a display element formed of the cured film according to claim 4. A spacer for a display element formed of the cured film according to claim 4. A color filter for a display element formed of the cured film according to claim 4. A liquid crystal display element comprising the insulating film for a display element according to claim 5. A liquid crystal display element comprising the display element spacer according to claim 6. A liquid crystal display element comprising the color filter for a display element according to claim 7. A process for producing an insulating film for a display element, comprising at least the following steps (A) to (D).
(A) a step of forming a film of the radiation sensitive composition according to any one of claims 1 to 3 on a substrate
(B) a step of exposing at least a part of the film to radiation
(C) Step of developing the film after exposure
(D) a step of heating the film after development A method for manufacturing a spacer for a display element, comprising at least the following steps (A) to (D).
(A) a step of forming a film of the radiation sensitive composition according to any one of claims 1 to 3 on a substrate
(B) a step of exposing at least a part of the film to radiation
(C) Step of developing the film after exposure
(D) a step of heating the film after development A manufacturing method of a color filter for a display element, comprising at least the following steps (A) to (D).
(A) a step of forming a film of the radiation sensitive composition according to any one of claims 1 to 3 on a substrate
(B) a step of exposing at least a part of the film to radiation
(C) Step of developing the film after exposure
(D) a step of heating the film after development A coloring composition comprising the copolymer [A], the polymerizable unsaturated compound [B], the compound [C], and the solvent and a colorant according to any one of claims 1 to 3.

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