KR101918433B1 - Resin composition, color filter and method for producing same, and image display element - Google Patents
Resin composition, color filter and method for producing same, and image display element Download PDFInfo
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- KR101918433B1 KR101918433B1 KR1020177020396A KR20177020396A KR101918433B1 KR 101918433 B1 KR101918433 B1 KR 101918433B1 KR 1020177020396 A KR1020177020396 A KR 1020177020396A KR 20177020396 A KR20177020396 A KR 20177020396A KR 101918433 B1 KR101918433 B1 KR 101918433B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
Abstract
A resin composition comprising an epoxy group and an acid group-containing resin (A), a polybasic acid monoester (B) containing a hydroxyl group-containing polyfunctional (meth) acrylate, and a solvent (C) And the epoxy group is 0.5 to 3.0 moles per mole.
Description
The present invention relates to a resin composition, a color filter, a manufacturing method thereof, and an image display device.
The color filter generally includes a transparent substrate such as a glass substrate, a red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundary between the pixels, And a protective film formed on the black matrix. A color filter having such a configuration is usually manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various methods have been proposed for forming the pixels and the black matrix (hereinafter, the pixel and the black matrix will be referred to as "coloring patterns"). However, various methods have been proposed, The pigment / dye dispersion method using lithography has become the current mainstream.
Generally, the photosensitive resin composition used for photolithography contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. The pigment / dye dispersion method has an advantage of being able to form a colored pattern having excellent durability such as light resistance and heat resistance and having few defects such as pinholes and the like. On the other hand, a pattern or a protective film of a black matrix, R, Therefore, a high solvent resistance is required for the cured coating film.
Thus, for example, a method of improving the solvent resistance by using a copolymer having an epoxy group or an oxetanyl group and a carboxyl group or a phenolic hydroxyl group (
In order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the coloring agent to be blended or to increase the film thickness. However, at the same time, these tend to have problems such as lowered sensitivity and lowered developing performance And further performance improvement is required (Patent Document 4).
However, the conventional photosensitive resin composition may not have sufficient sensitivity and developability, or may not have a cured coating film excellent in solvent resistance.
Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a resin composition which provides a cured coating film excellent in sensitivity and developability and excellent in solvent resistance. Another object of the present invention is to provide a color filter having a colored pattern formed of a cured coating film excellent in solvent resistance.
That is, the present invention is represented by the following [1] to [14].
[1] A resin composition comprising an epoxy group and an acid group-containing resin (A), a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B), and a solvent (C) ), The epoxy group is 0.5 to 3.0 moles relative to 1 mole of the acid group in the resin.
[2] The thermosetting resin composition as described in [1], wherein the epoxy group and the acid group-containing resin (A) comprise a monomer unit derived from a monomer (a-1) having in one molecule an ethylenic carbon- Resin composition.
[3] The resin composition according to [1] or [2], which contains a monomer unit derived from an unsaturated carboxylic acid (a-2) as a constituent monomer unit of the epoxy group and the acid group-containing resin (A).
[4] The resin composition according to any one of [1] to [4], wherein the epoxy group and the acid group-containing resin (A) are a mixture of a functional group reactive with a carboxyl group and a monomer having an ethylenic carbon- (a-3) contains a constituent monomer unit having an ethylenic carbon-carbon double bond added thereto.
[5] The resin composition according to [2], wherein the monomer (a-1) having one ethylenic carbon-carbon double bond and an epoxy group in one molecule is an epoxy group-containing (meth) acrylate.
[6] The resin composition according to any one of [1] to [3], wherein the monomer (a-3) having one ethylenic carbon-carbon double bond in one molecule is selected from (meth) Is at least one kind selected from the group consisting of the following.
The polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is preferably a polybasic acid monoester of di- or tri (meth) acrylate of pentaerythritol, a di- And a polybasic acid monoester of penta (meth) acrylate. The resin composition according to any one of [1] to [6]
[8] The resin composition according to any one of [1] to [7], wherein the acid value of the epoxy group- and acid group-containing resin (A) is 10 to 350 mgKOH / g.
[9] The resin composition according to any one of [1] to [8], further comprising a photopolymerization initiator (D).
[10] The resin composition according to any one of [1] to [9], further comprising a colorant (E).
[11] The resin composition according to [10], wherein the colorant (E) is at least one selected from the group consisting of dyes and pigments.
[12] A color filter having a colored pattern comprising a cured coating film of the resin composition according to [10] or [11].
[13] An image display device comprising the color filter according to [12].
[14] A method for producing a resin composition comprising the steps of applying a resin composition described in [10] or [11] onto a substrate, exposing and developing it with an aqueous alkali solution, and baking under a temperature condition of 215 캜 or less to form a colored pattern Gt;
According to the present invention, it is possible to provide a resin composition capable of forming a cured coating film excellent in sensitivity and developability and excellent in solvent resistance. The cured coating film in the state before baking after being formed from the resin composition of the present invention has a high developing property and thus has a very high value of use in various kinds of resist fields. Particularly, the cured coating film in the post baking state has excellent solvent resistance , And is useful for forming a coloring pattern of a color filter.
1 is a sectional view of a color filter which is one embodiment of the present invention.
The resin composition of the present invention comprises a resin (A) containing an epoxy group and an acid group, a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate, and a solvent (C) ), The amount of the epoxy group is 0.5 to 3.0 moles per mole of the acid group.
In the present invention, "(meth) acrylate" means at least one selected from methacrylate and acrylate. The same applies to "(meth) acrylic acid".
The epoxy group and acid group-containing resin (A) used in the present invention are not particularly limited as long as they have an epoxy group and an acid group in the resin, and the epoxy group is present in an amount of 0.5 to 3.0 moles per mole of the acid group in the resin. The acid group is not particularly limited, but usually includes a carboxyl group (-COOH), a phospho group (-PO (OH) 2 ), and a sulfo group (-SO 3 H). From the viewpoint of the curability of the resin composition of the present invention, a carboxyl group is preferable. From the viewpoints of ease of raw material availability, easiness of production of the epoxy group and acid group-containing resin (A), and improvement of the solvent resistance upon curing the resin composition of the present invention, one molecule of an ethylene- Is preferably a resin containing a monomer unit derived from the monomer (a-1) contained in the resin (a-1), and from the viewpoint of developing property, a resin further containing a monomer unit derived from the unsaturated carboxylic acid Is more preferable. The number of moles of the epoxy group with respect to 1 mole of the acid group of the epoxy group and the acid group-containing resin (A) can be calculated from the injection ratio of the constituent monomers when the kind and molar ratio of the constituent monomers are known. In the case of calculating the number of moles of the epoxy group per mole of the acid group from the epoxy group and the acid group-containing resin (A) after synthesis, the epoxy equivalent measured in accordance with JIS K 7236 and the acid value measured in accordance with JIS K 0070 are calculated.
As the monomer (a-1), an epoxy group-containing (meth) acrylate is preferable from the viewpoint of ease of production of the epoxy group and the acid group-containing resin (A). Specific examples of the monomer (a-1) include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate having an alicyclic epoxy group and a lactone adduct thereof (for example, (Meth) acrylate of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, dicyclopentenyl (meth) acrylate of dicyclopentenyl (meth) acrylate Epoxides of dicyclopentenyloxyethyl (meth) acrylate, and the like. Of these, glycidyl (meth) acrylate is particularly preferred from the viewpoints of ease of availability and reactivity.
Specific examples of the unsaturated carboxylic acid (a-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- Acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and the like. From the viewpoint of raw material availability, (meth) acrylic acid and crotonic acid are preferable, and (meth) acrylic acid is more preferable.
The epoxy group and the acid group-containing resin (A) used in the present invention may contain a monomer unit derived from a radically polymerizable monomer other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) . Specific examples of the radically polymerizable monomer other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) include dienes such as 2- (meth) acryloyloxyethyl acid phosphate and butadiene; Acrylates such as methyl (meth) acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) (Meth) acrylate, norbornyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (Meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (Meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, dicyclohexyl (meth) acrylate, (Meth) acrylate, adamantyl (meth) acrylate, (Meth) acrylates such as naphthalene (meth) acrylate; 2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, Tetracyclo [4.4.0.1 2,5 .1 7,10 ] dodeca-3-ene, dicyclopentadiene, tricyclo [5.2.1.0 2,6 ] deca-8-ene, tetracyclo [4.4.0.1 2 , 5,1 7,10 .0 1,6 ] dodeca-3-ene, pentacyclo [6.5.1.1 3,6 .0 2,7 .0 9,13 ] pentadeca- Boronene-2-carboxylic acid, 5-norbornene-2,3-dicarboxylic acid anhydride; (Meth) acrylic acid amides such as (meth) acrylic acid amide, (meth) acrylic acid N, N-diethylamide, (meth) acryl anthracenylamide, (meth) acrylic morpholine and diacetone (meth) acrylamide; Vinyl compounds such as (meth) acrylate anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and vinyltoluene; Styrene,? -, o-, m-, p-alkyl, nitro, cyano, amide derivatives of styrene; Unsaturated dicarboxylic acid diesters such as diethyl citraconate and diethyl maleate; Monomaleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; And unsaturated polybasic acid anhydrides such as maleic anhydride and itaconic anhydride. These may be used alone or in combination of two or more. Among them, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyl toluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate, Acrylate, norbornene, N-isopropyl (meth) acrylamide, (meth) acryl morpholine and diacetone (meth) acrylamide are preferable, and benzyl (meth) acrylate, dicyclopentanyl , Vinyl toluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate, and norbornene are more preferable.
The mixing ratio of the monomer (a-1) is not particularly limited as long as an epoxy group is present in an amount of 0.5 to 3.0 moles per mole of the acid group in the epoxy group and the acid group-containing resin (A) Is preferably 40 to 90 mol%, more preferably 50 to 90 mol%, and still more preferably 60 to 80 mol%, based on the total amount When the blend ratio of the monomer (a-1) is 40 to 90 mol%, the developability is satisfactory and sufficient solvent resistance is obtained.
The mixing ratio of the unsaturated carboxylic acid (a-2) is not particularly limited as long as an epoxy group is present in an amount of 0.5 to 3.0 moles per mole of the acid group in the epoxy group and the acid group-containing resin (A) Is preferably from 10 to 60 mol%, more preferably from 10 to 50 mol%, and still more preferably from 20 to 40 mol%, based on the total amount of the constituent monomers. When the blending ratio of the unsaturated carboxylic acid (a-2) is 10 to 60 mol%, the developing property is satisfactory and sufficient solvent resistance is obtained.
In the case of using a radically polymerizable monomer other than the monomer (a-1) and the unsaturated carboxylic acid (a-2), the compounding ratio thereof is not particularly limited, but the total amount of the constituent monomers of the epoxy group and the acid group- , Preferably not less than 0 mol% and not more than 50 mol%, more preferably not less than 0 mol% and not more than 40 mol%.
40 to 90% by mole of the monomer unit derived from the monomer (a-1) and 10% by mole of the monomer unit derived from the unsaturated carboxylic acid (a-2) relative to the total of the constituent monomer units of the epoxy group and the acid group- , More preferably 60 to 80 mol%, and more preferably 60 to 80 mol% of a monomer unit derived from the monomer (a-1) and 20 to 40 mol% of a monomer unit derived from the unsaturated carboxylic acid (a- Is more preferable.
The copolymerization reaction for producing the epoxy group and the acid group-containing resin (A) can be carried out according to a radical polymerization method known in the art. For example, a radically polymerizable monomer (optional component) other than the monomer (a-1), the unsaturated carboxylic acid (a-2), and the monomer (a-1) and the unsaturated carboxylic acid (a- , A polymerization initiator is added to the solution, and the reaction is carried out at 50 to 130 ° C for 1 to 20 hours. By this copolymerization reaction, a random copolymer having a monomer unit ratio substantially equivalent to that of the monomer is obtained.
Examples of the solvent that can be used in the copolymerization reaction include ethylene glycol monomethyl ether, triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, ethylene Ethylene glycol monoacetate, glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, Methyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether. These may be used alone or in combination of two or more.
The water content of the solvent is not particularly limited, but is preferably 1% by mass or less. When the water content is 1% by mass or less, an epoxy group and an acid group-containing resin (A) having better solvent resistance are obtained. The water content of the solvent can be measured by the Karl Fischer method under the following conditions.
Device: KF moisture meter MKA-520 manufactured by Kyoto Electronics Industry Co., Ltd.
Injection amount: 1 ml
Epitaxy: 3 mg of Aqua Micron (registered trademark) titrant SS (manufactured by APIC Corporation)
Electrode solution: Aqua Micron (registered trademark) dehydrating solvent PP (manufactured by API Co., Ltd.)
When the total amount of the constituent monomers of the epoxy group and the acid group-containing resin (A) is set to 100 parts by mass, the amount of the solvent to be used when preparing the epoxy group and the acid group-containing resin (A) is preferably 30 to 1000 Mass part, and more preferably 50 to 800 mass parts. Particularly, when the blending amount of the solvent is 1000 parts by mass or less, a decrease in the molecular weight of the epoxy group and the acid group-containing resin (A) is suppressed by the chain transfer action and the viscosity of the epoxy group and the acid group- can do. By setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, polymerization reaction can be performed stably, and coloring and gelation of the epoxy group and acid group-containing resin (A) can be prevented.
Examples of the polymerization initiator that can be used in the production of the epoxy group and acid group-containing resin (A) include, but not limited to, azobisisobutyronitrile, azobisisobalonitrile, benzoyl peroxide, Oxy-2-ethylhexanoate, and the like. These may be used alone or in combination of two or more.
The blending amount of the polymerization initiator is preferably 0.5 to 20 parts by mass, more preferably 1.0 to 10 parts by mass, when the total amount of the constituent monomers of the epoxy group and the acid group-containing resin (A) is 100 parts by mass.
In addition, radical polymerization (a-1) other than the monomer (a-1), the unsaturated carboxylic acid (a-2), and the optional monomer (a-1) and the unsaturated carboxylic acid The bulk polymerization may be carried out using a possible monomer and a polymerization initiator.
It is possible to further introduce an ethylenic carbon-carbon double bond into the epoxy group and the acid group-containing resin (A) obtained by the copolymerization reaction. This improves the sensitivity and developability of the resin composition.
For example, in a part of the carboxyl group derived from the unsaturated carboxylic acid (a-2) constituting the epoxy group and the acid group-containing resin (A), a functional group having reactivity with a carboxyl group and an ethylenic carbon- The monomer (a-3) may be added to introduce an ethylenic carbon-carbon double bond. As a result, the epoxy group and the acid group-containing resin (A) contain a monomer (a-3) having a functional group reactive with a carboxyl group and an ethylenic carbon-carbon double bond in one molecule in a part of the carboxyl group derived from the unsaturated carboxylic acid (a- Contains the constituent monomer unit having the added ethylenic carbon-carbon double bond. Examples of the functional group that reacts with the carboxyl group include an isocyanato group, an epoxy group, and a vinyl ether group. Among them, an isocyanato group is preferable from the viewpoint of reactivity in the addition reaction. As the monomer (a-3) having an epoxy group, those same as those exemplified as the monomer (a-1) can be used. The monomer (a-3) having an isocyanato group is not particularly limited, but isocyanato group-containing (meth) acrylate is preferable, and specific examples thereof include 2- (meth) acryloyloxyethyl Acrylate, isocyanate, 1,1- (bis (meth) acryloyloxymethyl) ethyl isocyanate and 2- (isocyanatoethyloxy) ethyl (meth) acrylate. Among them, a monomer having an isocyanato group and an ethylenic carbon-carbon double bond in one molecule is preferable, and 2- (meth) acryloyloxyethyl isocyanate is more preferable. The monomer (a-3) having a vinyl ether group is not particularly limited, but vinyl ether (meth) acrylate is preferable, and specifically, 2- (2-vinyloxyethoxy) ethyl methacrylate and the like .
When the epoxy group and the acid group-containing resin (A) contain an acid anhydride group, a monomer having an ethylenic carbon-carbon double bond in one molecule is added to a functional group which reacts with an acid anhydride group to form an ethylenic carbon- . Examples of the functional group that reacts with the acid anhydride group include a hydroxyl group.
The reaction of adding a monomer having a reactive functional group to a carboxyl group, an epoxy group or an acid anhydride group in the epoxy group and the acid group-containing resin (A) to introduce a carbon-carbon double bond is added to the epoxy group and the acid group- The reaction may be carried out by adding the monomer, the polymerization inhibitor and the catalyst, preferably at 50 to 150 ° C, more preferably at 80 to 130 ° C. Further, in this addition reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included, so that the addition reaction can be carried out without removing the solvent after completion of the copolymerization reaction.
Here, the polymerization inhibitor may be added in order to prevent gelation by polymerization of the epoxy group and the acid group-containing resin (A). Examples of the polymerization inhibitor include, but are not limited to, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and the like. Examples of the catalyst include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, chelate compounds of chromium And the like.
The acid value (JIS K 6901: 2008 5.3.2) of the epoxy group and acid group-containing resin (A) used in the present invention is not particularly limited, but is preferably 10 to 350 mgKOH / g when used for color filter applications More preferably 30 to 200 mgKOH / g, still more preferably 50 to 180 mgKOH / g, and particularly preferably 70 to 150 mgKOH / g. When the acid value is 10 mgKOH / g or more, sufficient developability is obtained. On the other hand, if the acid value is 350 mgKOH / g or less, the exposed portion (photo-cured portion) is not dissolved in the alkaline developer, and sufficient developability is obtained.
The molecular weight (weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) described later) of the epoxy group and acid group-containing resin (A) is preferably 1000 to 50000, more preferably 3000 ~ 40000. When the molecular weight is 1000 or more, the coloring pattern is not defected after development and good sensitivity is obtained. On the other hand, if the molecular weight is 50,000 or less, the development time is sufficiently short and practical.
When the epoxy group and the acid group-containing resin (A) have an unsaturated group, the unsaturated group equivalent is not limited, but is preferably 100 to 4000 g / mol, and more preferably 200 to 3000 g / mol. When the equivalent of the unsaturated group is 100 g / mol or more, it is effective in further improving the heat decomposition resistance and the heat resistance sulfur deformation. On the other hand, if the unsaturated group equivalent is 4000 g / mol or less, it is effective to increase the sensitivity.
The resin composition of the present invention contains a polybasic acid monoester (B) having a hydroxyl group-containing polyfunctional (meth) acrylate. Examples of the polybasic acid monoesters (B) of the hydroxyl group-containing polyfunctional (meth) acrylate include polybasic acid monoesters of di- or tri (meth) acrylates of pentaerythritol, di- And polybasic acid monoesters of penta (meth) acrylate. Specific examples thereof include modified products of dipentaerythritol pentaacrylate succinate, modified pentaerythritol triacrylate succinic acid, modified products of dipentaerythritol pentaacrylate phthalic acid , Modified polybasic acid obtained by adding an acid anhydride to the hydroxyl group of a hydroxyl group-containing polyfunctional (meth) acrylate such as pentaerythritol triacrylate phthalic acid modified product. These may be used alone or in combination of two or more. Among them, a succinic acid-modified product of a hydroxyl group-containing polyfunctional (meth) acrylate is preferable from the viewpoint of solvent resistance.
The blending amount of the polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is preferably 10 to 90 mass%, more preferably 20 to 90 mass%, based on the total of the components (A) 80% by mass, and more preferably from 25% to 70% by mass. When the amount is within this range, a resin composition having an appropriate viscosity is obtained, and the photopolymerization initiator (D) to be described later is blended to have appropriate photocurability.
The resin composition of the present invention contains a solvent (C). The solvent (C) is not particularly limited as long as it is an inert solvent which dissolves the epoxy group and acid group-containing resin (A) and the polybasic acid monoester (B) containing a hydroxyl group-containing polyfunctional (meth) acrylate and does not react with them.
As the solvent (C), the same solvent as used for the copolymerization reaction in the production of the epoxy group and acid group-containing resin (A) may be used, and the solvent contained after the copolymerization reaction may be used as it is. May be added at the time of preparation of the resin composition of the present invention. Alternatively, when other components to be described later are added, a solvent coexisting with these components may be used as it is. Specific examples of the solvent (C) include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate, isopropyl acetate, dipropylene glycol monomethyl ether, There may be mentioned glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethylene glycol monoethyl ether acetate and diethylene glycol monoethyl ether acetate . These may be used alone or in combination of two or more. Of these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate which are used in the copolymerization reaction in the production of the epoxy group and acid group-containing resin (A) are preferable.
The blending amount of the solvent (C) is preferably from 30 to 1000 parts by mass, more preferably from 50 to 800 parts by mass, and more preferably from 50 to 800 parts by mass, based on 100 parts by mass of the total of components excluding the solvent (C) More preferably 100 to 700 parts by mass. When the amount is in this range, a resin composition having an appropriate viscosity is obtained.
When the resin composition of the present invention is used for forming a coloring pattern of a color filter, a photo polymerization initiator (D) and a colorant (E) are further blended and used.
Examples of the photopolymerization initiator (D) include, but are not limited to, benzoin such as benzoin and benzoin methyl ether and alkyl ethers thereof; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone and 4- (1-t-butyldioxy-1-methylethyl) acetophenone; Alkylphenols such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Anthraquinones such as 2-methyl anthraquinone, 2-amylanthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone and 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; (2-methylbenzoyl) -9H-carbaldehyde, 1- [4- (phenylthio) -, 2- Oxazol-3-yl] -, 1- (O-acetyloxime); 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide; And xanthones. These may be used alone or in combination of two or more.
The blending amount of the photopolymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass, and more preferably from 0.5 to 20 parts by mass, based on 100 parts by mass of the sum of the components (A) and (B) Is 1 to 15 parts by mass. When the amount is within this range, a resin composition having suitable photocurability is obtained.
The colorant (E) is not particularly limited as long as it is soluble or dispersible in the resin composition of the present invention, and examples thereof include dyes and pigments.
Particularly, in the resin composition of the present invention, sufficient solvent resistance can be obtained even if baking is performed at a relatively low temperature (215 캜 or less) as described later, which makes it difficult to cause deterioration of the dye due to heat. Therefore, in the resin composition of the present invention, more kinds of dyes can be freely used to obtain a colored pattern.
From the viewpoints of solubility or dispersibility in the resin composition of the present invention, interaction with other components in the resin composition, heat resistance, etc., the dyes include acid dyes having acidic groups such as carboxyl groups, salts with nitrogen compounds of acid dyes, It is preferable to use a sulfonamide form of an acidic dye or the like. Examples of such dyes include,
And derivatives thereof. Among them, preferred are azo dyes, xanthan dyes, anthraquinone dyes or phthalocyanine dyes. These can be used alone or in combination of two or more kinds depending on the color of the target pixel.
Examples of pigments include C.I.
Further, the dye and the pigment may be used in combination depending on the color of a target pixel.
When the colorant (E) is blended, the blending amount thereof is preferably 5 to 80 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the total of components excluding the solvent (C) in the resin composition of the present invention, 70 parts by mass, and more preferably 10 to 60 parts by mass.
When a pigment is used as the colorant (E), a known dispersant may be added to the resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersing agent, it is preferable to use a polymer dispersing agent having excellent dispersion stability over time. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified ester-based dispersant. Examples of such a polymer dispersant include EFKA (registered trademark, manufactured by BASF), Disperbyk (registered trademark, manufactured by Big Chem Japan Co., Ltd.), Diparron (registered trademark, manufactured by Cusmotor Co., Those sold under the trade names of SOLSPERSE (registered trademark, manufactured by Lubrizol Corporation) may be used.
The blending amount of the dispersing agent may be appropriately set depending on the kind of the pigment to be used and the like.
When the resin composition of the present invention is used for the formation of a coloring pattern of a color filter, it is preferable to use a resin (A) containing an epoxy group and an acid group, a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) The blending amount of the polymerization initiator (D) and the colorant (E) is preferably 90 to 10% by mass, the content of the epoxy group and the acid group-containing resin (A) in the total of the components (A) (C) is from 30 to 1000 parts by mass, (A) from 10 to 90% by mass of the polybasic acid monoester (B) of the functional (meth) acrylate and the sum of the components excluding the solvent (E) is 5 to 30 parts by mass based on 100 parts by mass of the total of the component (A) and the component (B), when the total amount of the components excluding the solvent (C) To 80 parts by mass, and more preferably, the total of the components (A) and (B) (B) of 80 to 20 mass%, the polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate is contained in an amount of 20 to 80 mass%, the content of the epoxy group and the acid group- (C) and 50 to 800 parts by mass of the total of the components (A) and (B) is 100 parts by mass, the content of the photopolymerization initiator (D) is 0.5 to 20 parts by mass, The amount of the colorant (E) is preferably 5 to 70 parts by mass, more preferably the content of the epoxy group and the acid group (B) is 5 to 70 parts by mass relative to the sum of the components (A) and The total amount of the components excluding the solvent (C) in the resin composition is set to 100 parts by mass, the content of the resin (A) is 75 to 30% by mass, the amount of the polybasic acid monoester (B) , The solvent (C) is 100 to 700 parts by mass, the total of the components (A) and (B) Is a photopolymerization initiator (D) is 1 to 15 parts by weight, the resin composition solvent (C) is 10 - coloring agent (E) if the total of the components except 100 parts by weight of 60 parts by weight if 100 parts by weight.
Even when the resin composition of the present invention does not contain the colorant (E), the resin (A) containing an epoxy group and the acid group, the polybasic acid monoester (B) of a hydroxyl group- containing polyfunctional (meth) acrylate, The above values are applicable to the blending amount of the initiator (D).
Similarly, even when the resin composition of the present invention does not contain the photopolymerization initiator (D) and the colorant (E), the resin (A) containing an epoxy group and the acid group, the polybasic acid monoesters of a hydroxyl group-containing polyfunctional (meth) B) and the solvent (C), the above values are applicable.
In addition to the above-mentioned components, known additives such as known coupling agents, leveling agents and thermal polymerization inhibitors may be added to the resin composition of the present invention in order to impart predetermined characteristics. The blending amount of these additives is not particularly limited as long as the effect of the present invention is not impaired.
The resin composition of the present invention can be produced by using a known mixing apparatus and mixing the above components.
The resin composition of the present invention is obtained by first preparing a resin composition containing an epoxy group and an acid group-containing resin (A), a polybasic acid monoester (B) having a hydroxyl group-containing polyfunctional (meth) acrylate and a solvent (C) A polymerization initiator (D) and an optional colorant (E). Further, the resin composition of the present invention can be used for forming a coloring pattern of a color filter as well as for other purposes.
Since the resin composition of the present invention thus obtained has alkali developability, development can be carried out by using an aqueous alkali solution. In particular, the resin composition of the present invention can provide a cured coating film excellent in sensitivity and developability and excellent in solvent resistance. Therefore, the resin composition of the present invention is suitable for use as a resist used for forming a color pattern of a color filter to be attached to various resists, particularly, an organic EL display, a liquid crystal display, and a solid-state image pickup device. Further, since the resin composition of the present invention provides a cured coating film excellent in properties such as solvent resistance, it can be used for various coatings, adhesives, binders for printing inks, and the like.
Next, a color filter manufactured by using the resin composition of the present invention will be described. The color filter of the present invention has a coloring pattern obtained from the resin composition.
Hereinafter, a color filter according to an embodiment of the present invention will be described with reference to the drawings.
1 is a cross-sectional view of a color filter according to an embodiment of the present invention. 1, the color filter includes a
Next, a method of manufacturing a color filter according to an embodiment of the present invention will be described.
First, a colored pattern is formed on the
The coloring pattern can be formed by using photolithography. Specifically, after the resin composition is applied on the
The method of applying the resin composition is not particularly limited, but a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, or the like can be used. After the application of the resin composition, if necessary, volatile components such as the solvent (C) may be volatilized by heating using a heating means such as a circulating oven, an infrared heater, or a hot plate. The heating conditions are not particularly limited and may be appropriately set depending on the kind of the resin composition to be used. Generally, it may be heated at a temperature of 50 ° C to 120 ° C for 30 seconds to 30 minutes.
A light source used for exposure is not particularly limited, but a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like can be used. The amount of exposure is not particularly limited and may be suitably adjusted according to the kind of the resin composition to be used.
The alkali aqueous solution used for development is not particularly limited, and examples thereof include aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like; An aqueous solution of an amine compound such as ethylamine, diethylamine or dimethylethanolamine; 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 3-methyl-4-amino-N-ethyl-N -? - methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate salts thereof And the like can be used. Among them, it is preferable to use an aqueous solution of a p-phenylenediamine compound. To these aqueous solutions, a defoaming agent or a surfactant may be added as necessary. Further, it is preferable to rinse with water after developing with the alkali aqueous solution.
The baking conditions are not particularly limited and may be subjected to heat treatment depending on the type of the resin composition to be used. By using the resin composition of the present invention, baking can be performed at a lower temperature than in the prior art, And more preferably at 130 to 215 캜 for 10 to 60 minutes. A sufficient solvent resistance can be obtained even at a baking temperature lower than the conventional one, so that it is possible to use even more dyes which can not be used as a problem of deterioration due to heat.
A desired coloring pattern can be formed by repeating the above-described application, exposure, development and baking in sequence using the resin composition for the
In the above description, a method of forming a colored pattern by photo-curing has been described. However, when a resin composition containing a curing accelerator and a known epoxy resin is used in place of the photo-polymerization initiator (D) , And a desired coloring pattern may be formed by heating.
Next, the
The color filter manufactured in this way has a coloring pattern excellent in solvent resistance because it is produced using a resin composition which provides a cured coating film excellent in sensitivity and developability and excellent in solvent resistance.
Example
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this embodiment, all parts and percentages are on a mass basis unless otherwise specified. Also, the acid value of the epoxy group and the acid value of the acid group-containing resin (A) measured according to JIS K 6901: 2008 5.3.2 is required to neutralize the acid component contained in 1 g of the epoxy group and the acid group-containing resin (A) &Quot; means the number of mg of potassium hydroxide. The weight average molecular weight means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) under the following conditions.
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko K.K.)
Column temperature: 40 DEG C
Sample: 0.2% tetrahydrofuran solution of resin
Developing solvent: tetrahydrofuran
Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko K.K.)
Flow rate: 1 ml / min
≪ Synthesis Example 1 &
324 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, stirred while replacing nitrogen gas, and heated to 80 캜. Subsequently, 17 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile (2-methoxyethyl) acrylate) was added to a monomer mixture consisting of 86 parts by mass of methacrylic acid (1 mole) and 71 parts by mass (0.5 mole) of glycidyl methacrylate ) (Polymerization initiator, V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added to the flask over a period of 2 hours from the dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 80 캜 for 2 hours to carry out a copolymerization reaction to obtain a resin-containing liquid No. 1 (solid dispersion value: 320 mgKOH / g, weight average molecular weight: 10000). The number of moles of the epoxy group per mol of the acid in the resin-containing liquid obtained was 0.5.
≪ Synthesis Examples 2 to 5 &
As shown in Table 1, except that the amounts of propylene glycol monomethyl ether acetate (PGMEA), methacrylic acid (MAa) and glycidyl methacrylate (GMA) were changed, To 5 was obtained.
≪ Synthesis Example 6 &
470 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, stirred while replacing nitrogen gas, and heated to 80 캜. Subsequently, 25 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) was added to a monomer mixture comprising 86 parts by mass (1 mole) of methacrylic acid and 142 parts by mass (1 mole) of glycidyl methacrylate ) (Polymerization initiator, V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added to the flask over a period of 2 hours from the dropping funnel. After completion of the dropwise addition, the copolymerization reaction was further carried out at 80 DEG C for 2 hours with stirring.
Subsequently, at 60 캜, 0.1 part by mass of dibutyltin laurate (catalyst, manufactured by Wako Pure Chemical Industries, Ltd.) and 2-isocyanatoethyl methacrylate (manufactured by Showa Denko KK) (78 parts by mass) After stirring for 1 hour, 160 parts by mass of propylene glycol monomethyl ether acetate was added to obtain a resin-containing liquid No. 6 (solid dispersion value: 85 mgKOH / g, weight average molecular weight: 13000). The number of moles of the epoxy group with respect to 1 mole of the acid in the obtained resin-containing liquid was 2.
≪ Synthesis Example 7 &
977 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introducing tube, stirred while replacing nitrogen gas, and heated to 80 ° C. Subsequently, 52 parts by mass of 2,2-azobis (meth) acrylate was added to a monomer mixture composed of 86 parts by mass (1 mole) of methacrylic acid, 104 parts by mass (1 mole) of styrene and 284 parts by mass (2 mole) of glycidyl methacrylate (2,4-dimethylvaleronitrile) (polymerization initiator, V-65 manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the flask over 2 hours from the dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 80 占 폚 for 2 hours to carry out a copolymerization reaction to obtain a resin-containing liquid No. 7 (solid dispersion value: 120 mgKOH / g, weight average molecular weight: 8000). The number of moles of the epoxy group with respect to 1 mole of the acid in the obtained resin-containing liquid was 2.
≪ Preparation of Resin Composition >
The resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were prepared by changing the kinds of the resin-containing liquid and the polymerizable monomer as shown in Tables 3 and 4 with the blend shown in Table 2 as the basic blend.
≪ Evaluation of solvent resistance &
The solvent resistance to N-methyl-2-pyrrolidone (NMP) which is a solvent generally used in the protective film forming step of the color filter was evaluated.
The prepared resin composition was spin-coated on a glass substrate (non-alkali glass substrate) having a width of 5 cm and a thickness of 2.5 μm after baking at 210 ° C, followed by heating at 90 ° C for 3 minutes to volatilize the solvent. Next, the coated film was exposed to light having a wavelength of 365 nm (exposure amount: 300 mJ / cm 2), and the exposed portion was photo-cured, and then left in a dryer at a baking temperature of 210 캜 for 20 minutes to prepare a cured coating film. Using a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation), the transmittance of the test piece on which the cured coating film was formed was measured at a wavelength of 675 nm. Subsequently, 55 parts by mass of N-methyl-2-pyrrolidone (NMP) was placed in a chalet with a lid attached thereto, and a test piece having a cured coating film was immersed therein. The results are shown in Table 5. The increase of the transmittance means that the colorant is eluted into N-methyl-2-pyrrolidone (NMP), and the difference between the initial transmittance and the transmittance after N-methyl-2-pyrrolidone It can be said that the solvent resistance is high.
<Evaluation of Alkali Developability>
The prepared resin composition was spin-coated on a glass substrate (non-alkali glass substrate) having a width of 5 cm and a thickness of 2.5 탆, and then heated at 90 캜 for 3 minutes to volatilize the solvent. Next, a photomask of a predetermined pattern was disposed at a distance of 100 mu m from the coated film, and the coated film was exposed through the photomask (exposure amount: 150 mJ / cm < 2 >) and the exposed portion was photo-cured. Next, an unexposed portion was dissolved by an aqueous solution containing 0.1% by mass of sodium carbonate by spraying at a temperature of 23 캜 and a pressure of 0.3 MPa to develop and then baked at 210 캜 for 30 minutes to form a predetermined pattern, The residue was confirmed. The residue after the alkali development was confirmed by observing the pattern after the alkali development using an electron microscope S-3400 (manufactured by Hitachi High-Technologies Corporation). The evaluation criteria are as follows. The results are shown in Table 5.
○: No residue
X: Residual
≪ Evaluation of sensitivity &
The alkaline development using the spray was performed for 30 seconds, and the amount of decrease in the pattern thickness before and after the alkali development was measured with a touching step level meter ET4000M (manufactured by Kosaka Laboratory). This pattern thickness, as the reduction amount is smaller, can be said that the sensitivity is good, and the evaluation criteria are as follows. The results are shown in Table 5.
?: Less than 0.20 占 퐉
X: 0.20 탆 or more
As can be seen from the results in Table 5, when the resin compositions of Examples 1 to 10 were used, a cured coating film having good developability and sensitivity and excellent solvent resistance was provided, while the resin compositions of Comparative Examples 1 to 7 The solvent resistance was not sufficient.
Industrial availability
As can be seen from the above results, according to the present invention, it is possible to provide a resin composition capable of forming a cured coating film having satisfactory sensitivity and developability as well as sufficient solvent resistance. Therefore, the resin composition of the present invention is preferable as a resist for a color filter. Further, by using the resin composition of the present invention, a color filter having a coloring pattern excellent in solvent resistance and having high reliability can be obtained.
1: substrate,
2: pixel,
3: Black Matrix,
4: Shield.
Claims (14)
The resin composition contains a monomer unit derived from the monomer (a-1) having, in one molecule, an ethylenic carbon-carbon double bond and an epoxy group as constituent monomer units of the epoxy group and the acid group-containing resin (A).
The resin composition containing the monomer unit derived from the unsaturated carboxylic acid (a-2) as the constituent monomer unit of the epoxy group and the acid group-containing resin (A).
Wherein the epoxy group and the acid group-containing resin (A) contain a functional group reactive with a carboxyl group and a monomer (a-2) having in one molecule an ethylenic carbon-carbon double bond in a part of the carboxyl group derived from the unsaturated carboxylic acid (a- 3) a structural monomer unit having an ethylenic carbon-carbon double bond added thereto.
Wherein the monomer (a-1) having one ethylenic carbon-carbon double bond and an epoxy group in one molecule is an epoxy group-containing (meth) acrylate.
Wherein the monomer (a-3) having one ethylenic carbon-carbon double bond in one molecule and a functional group reacting with the carboxyl group is at least one selected from the group consisting of an epoxy group-containing (meth) acrylate and an isocyanato group- Or two or more thereof.
Wherein the polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is at least one selected from the group consisting of polybasic acid monoesters of di- or tri (meth) acrylates of pentaerythritol, di- tri-, tetra- or penta ) Acrylate monobasic acid monoesters. ≪ RTI ID = 0.0 > 1 < / RTI >
And the acid value of the epoxy group and acid group-containing resin (A) is 10 to 350 mgKOH / g.
A resin composition further comprising a photopolymerization initiator (D).
And a colorant (E).
Wherein the colorant (E) is at least one selected from the group consisting of dyes and pigments.
And baking at a temperature of 215 DEG C or less to form a colored pattern.
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| PCT/JP2015/078473 WO2016103844A1 (en) | 2014-12-25 | 2015-10-07 | Resin composition, color filter and method for producing same, and image display element |
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| KR102321087B1 (en) * | 2018-11-23 | 2021-11-02 | 주식회사 엘지화학 | Photosensitive resin composition, photoresist, color filter and display device |
| KR20230071160A (en) | 2020-09-23 | 2023-05-23 | 스미또모 베이크라이트 가부시키가이샤 | Polymers, polymer solutions and photosensitive resin compositions |
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| JP5187492B2 (en) * | 2007-11-22 | 2013-04-24 | Ｊｓｒ株式会社 | Curable resin composition, protective film and method for forming protective film |
| JP5454285B2 (en) * | 2009-04-28 | 2014-03-26 | Ｊｓｒ株式会社 | DYE-SENSITIZED SOLAR CELL ELECTRODE, RESIN COMPOSITION FOR FORMING SHIELD FILM OF DYE-SENSITIZED SOLAR CELL ELECTRODE, SHIELD FILM AND METHOD FOR FORMING THE SAME |
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| JP2013228727A (en) * | 2012-03-29 | 2013-11-07 | Mitsubishi Chemicals Corp | Color filter coloring resin composition, color filter, liquid crystal display device, and organic el display device |
| JP6031901B2 (en) * | 2012-09-06 | 2016-11-24 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring composition, colored film and color filter |
| JP2014134763A (en) * | 2012-12-11 | 2014-07-24 | Jsr Corp | Radiation-sensitive resin composition, cured film for display element, method for forming cured film for display element, and display element |
| KR102115817B1 (en) * | 2013-01-16 | 2020-05-27 | 제이에스알 가부시끼가이샤 | Thermosetting resin composition for forming cured film, negative radiation-sensitive resin composition, positive radiation-sensitive resin composition, cured film, method for forming the same, semiconductor device and display device |
| JP6048670B2 (en) * | 2013-03-27 | 2016-12-21 | Jsr株式会社 | Radiation sensitive resin composition |
| JP2014197155A (en) * | 2013-03-29 | 2014-10-16 | 富士フイルム株式会社 | Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic electroluminescence (el) display device |
| JP2014215954A (en) * | 2013-04-30 | 2014-11-17 | 新日鉄住金化学株式会社 | Photosensitive resin composition for forming touch panel insulating film and protective film, and touch panel obtained using the same |
-
2015
- 2015-10-07 JP JP2016565974A patent/JPWO2016103844A1/en active Pending
- 2015-10-07 CN CN201580070146.6A patent/CN107108769B/en active Active
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2921770B2 (en) | 1991-01-17 | 1999-07-19 | 日本化薬株式会社 | Resin composition for color filter protective film and cured product thereof |
| JP2013164471A (en) * | 2012-02-09 | 2013-08-22 | Jsr Corp | Curable resin composition, cured film for display device, formation method of cured film for display device, and display device |
| JP2014152192A (en) | 2013-02-05 | 2014-08-25 | Jsr Corp | Thermosetting resin composition for forming cured film, radiation-sensitive resin composition for forming cured film, cured film, method for forming the same, semiconductor element, and display element |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20170097757A (en) | 2017-08-28 |
| TWI600970B (en) | 2017-10-01 |
| JPWO2016103844A1 (en) | 2017-10-05 |
| CN107108769B (en) | 2019-02-19 |
| CN107108769A (en) | 2017-08-29 |
| WO2016103844A1 (en) | 2016-06-30 |
| TW201631396A (en) | 2016-09-01 |
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