WO2016103844A1 - 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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- WO2016103844A1 WO2016103844A1 PCT/JP2015/078473 JP2015078473W WO2016103844A1 WO 2016103844 A1 WO2016103844 A1 WO 2016103844A1 JP 2015078473 W JP2015078473 W JP 2015078473W WO 2016103844 A1 WO2016103844 A1 WO 2016103844A1
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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
- 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
- C08F265/04—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
Definitions
- the present invention relates to a resin composition, a color filter, a manufacturing method thereof, and an image display element.
- the color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the pixel boundary, It is comprised from the protective film formed on a pixel and a 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 as a method for forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as a “colored pattern”).
- a photosensitive resin composition as a resist
- a 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 the advantage of being able to form a colored pattern that is excellent in durability such as light resistance and heat resistance and has few defects such as pinholes, but the black matrix, R, G, and B patterns. Since the protective film is repeatedly formed, the cured coating film is required to have high solvent resistance.
- Patent Documents 1 and 2 methods for improving solvent resistance using a copolymer having an epoxy group or oxetanyl group and a carboxyl group or a phenolic hydroxyl group (Patent Documents 1 and 2) and an oxadi having a trihalomethyl group as a polymerization initiator
- Patent Document 3 A method for improving solvent resistance using a molecule containing a molecule having an azole structure or a triazine structure has been proposed.
- Patent Document 4 in order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the colorant to be blended or to increase the film thickness. However, these simultaneously reduce sensitivity, developability, etc. Therefore, further performance improvement is required (Patent Document 4).
- the conventional photosensitive resin composition may not have sufficient sensitivity and developability, or a cured coating film having excellent solvent resistance may not be obtained. Accordingly, the present invention has been made to solve the above-described problems, and provides a resin composition that provides a cured coating film having good sensitivity and developability and excellent solvent resistance. With the goal. Moreover, an object of this invention is to provide the color filter which has a coloring pattern which consists of a cured coating film excellent in solvent resistance.
- a resin composition comprising an epoxy group- and acid group-containing resin (A), a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate, and a solvent (C), A resin composition characterized in that the epoxy group is 0.5 to 3.0 mol per 1 mol of the acid group in the epoxy group and acid group-containing resin (A).
- a resin composition Containing a monomer unit derived from the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule as constituent monomer units of the epoxy group- and acid group-containing resin (A) The resin composition according to [1].
- the epoxy group- and acid group-containing resin (A) is a part of the carboxyl group derived from the unsaturated carboxylic acid (a-2), a functional group that reacts with the carboxyl group, and an ethylenic carbon-carbon double
- the resin composition according to [3] comprising a constituent monomer unit having an ethylenic carbon-carbon double bond to which a monomer (a-3) having a bond in one molecule is added.
- the resin composition according to [2], wherein the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule is an epoxy group-containing (meth) acrylate.
- the monomer (a-3) having in one molecule a functional group that reacts with the carboxyl group and an ethylenic carbon-carbon double bond is an epoxy group-containing (meth) acrylate and isocyanato group-containing (meth) acrylate.
- the polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is a dibasic acid monoester of pentaerythritol, a dibasic acid monoester of tri (meth) acrylate, dipentaerythritol di, tri, tetra, or
- An image display device comprising the color filter according to [12].
- [14] Applying the resin composition according to [10] or [11] on a substrate, exposing and developing with an alkaline aqueous solution, and baking at a temperature of 215 ° C. or lower to form a colored pattern A method for producing a color filter.
- a resin composition capable of forming a cured coating film having good sensitivity and developability and excellent solvent resistance. Further, a cured coating film in a state after exposure and before baking formed from the resin composition of the present invention has extremely high utility value in various resist fields because it has developability, and particularly in a cured coating state after baking. Since the film is excellent in solvent resistance, it is useful for forming a colored pattern of a color filter.
- the resin composition of the present invention contains an epoxy group- and acid group-containing resin (A), a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate, and a solvent (C), and an epoxy group.
- the epoxy group is 0.5 to 3.0 mol with respect to 1 mol of the acid group in the acid group-containing resin (A).
- (meth) acrylate means at least one selected from methacrylate and acrylate.
- (meth) acrylic acid means at least one selected from methacrylate and acrylate.
- the epoxy group and acid group-containing resin (A) used in the present invention has an epoxy group and an acid group in the resin, and the epoxy group is 0.5 to 3.0 per mol of the acid group in the resin.
- the acid group is not particularly limited, and usually includes a carboxyl group (—COOH), a phospho group (—PO (OH) 2 ), a sulfo group (—SO 3 H) and the like. From the viewpoint of curability of the resin composition of the present invention, a carboxyl group is preferred.
- a resin containing a monomer unit derived from the monomer (a-1) having a heavy bond and an epoxy group in one molecule is preferable.
- an unsaturated carboxylic acid (a-2) It is more preferable that the resin further contains a monomer unit derived from.
- 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 charging ratio of the constituent monomer when the kind and mole ratio of the constituent monomer are known. it can.
- the monomer (a-1) is preferably an epoxy group-containing (meth) acrylate from the viewpoint of ease of production of the epoxy group- and 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 (eg, a cyclomer manufactured by Daicel Corporation).
- the unsaturated carboxylic acid (a-2) include (meth) acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, fumaric acid, vinyl sulfonic acid, 2- (meth) acryloyloxyethyl succinic acid 2-acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, and the like. From the viewpoint of obtaining raw materials, (meth) acrylic acid and crotonic acid are preferable, and (meth) acrylic acid is more preferable.
- the epoxy group and acid group-containing resin (A) used in the present invention contains monomer units derived from radically polymerizable monomers other than monomer (a-1) and unsaturated carboxylic acid (a-2) as constituent monomer units. May be.
- Specific examples of the monomer capable of radical polymerization other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) include 2- (meth) acryloyloxyethyl acid phosphate, dienes such as butadiene; methyl (meth) Acrylate, isopropyl (meth) acrylate, pentyl (meth) acrylate, benzyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, 1,4- Cyclohexanedimethanol mono (meth) acrylate,
- benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyltoluene, isobornyl (meth) acrylate, adamantyl (meth) acrylate, norbornene, N- Isopropyl (meth) acrylamide, (meth) acryl morpholine, and diacetone (meth) acrylamide are preferred
- benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, styrene, vinyltoluene, isobornyl (meth) acrylate, adamantyl (Meth) acrylate and norbornene are more preferred.
- the blending ratio of the monomer (a-1) is not particularly limited as long as the 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 acid group-containing resin (A)
- the amount is preferably 40 to 90 mol%, more preferably 50 to 90 mol%, still more preferably 60 to 80 mol%, based on the total of the constituent monomers of the epoxy group and acid group-containing resin (A).
- the blending ratio of the monomer (a-1) is 40 to 90 mol%, the developability is good and sufficient solvent resistance is obtained.
- the blending ratio of the unsaturated carboxylic acid (a-2) is not particularly limited as long as 0.5 to 3.0 mol of epoxy groups are present per 1 mol of acid groups in the epoxy group and acid group-containing resin (A). However, it is preferably 10 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol based on the total of the constituent monomers of the epoxy group and acid group-containing resin (A). %. When the blending ratio of the unsaturated carboxylic acid (a-2) is 10 to 60 mol%, the developability is good and sufficient solvent resistance is obtained.
- the mixing ratio is not particularly limited, but the constituent monomer of the epoxy group- and acid group-containing resin (A) Preferably, it is more than 0 mol% and 50 mol% or less, and more preferably more than 0 mol% and 40 mol% or less.
- 40 to 90 mol% of monomer units derived from monomer (a-1) and monomer units derived from unsaturated carboxylic acid (a-2) with respect to the total of constituent monomer units of epoxy group and acid group-containing resin (A) Is more preferably 10 to 60 mol%, the monomer unit derived from the monomer (a-1) is 60 to 80 mol%, and the monomer unit derived from the unsaturated carboxylic acid (a-2) is 20 to 40 mol%. It is more preferable to contain.
- the copolymerization reaction for producing the epoxy group- and acid group-containing resin (A) can be performed according to a radical polymerization method known in the art.
- monomer (a-1), unsaturated carboxylic acid (a-2), and a monomer (optional component) capable of radical polymerization other than monomer (a-1) and unsaturated carboxylic acid (a-2) are used as a solvent.
- a polymerization initiator may be added to the solution and reacted at 50 to 130 ° C. for 1 to 20 hours.
- a random copolymer having a monomer unit ratio substantially equal to the monomer mixing ratio is obtained.
- Examples of the solvent that can be used for 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 glycol monobutyl ether, and diethylene glycol monomethyl ether.
- Hexyl ether ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol mono Chill ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether. These can be used alone or in combination of two or more.
- the moisture content of a solvent is not specifically limited, It is preferable that it is 1 mass% or less. When the water content is 1% by mass or less, an epoxy group- and acid group-containing resin (A) having better solvent resistance can be obtained.
- the water content of the solvent can be measured by the Karl Fischer method under the following conditions. Apparatus: Kyoto Electronics Industry Co., Ltd., KF moisture meter MKA-520 Injection volume: 1 mL Titration solution: Aquamicron (registered trademark) titrant SS3 mg (manufactured by API Corporation) Electrode solution: Aquamicron (registered trademark) dehydrated solvent PP (manufactured by API Corporation)
- the blending amount of the solvent in producing the epoxy group and acid group-containing resin (A) is not particularly limited, but when the total of the constituent monomers of the epoxy group and acid group-containing resin (A) is 100 parts by mass, The amount is preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass. In particular, by setting the blending amount of the solvent to 1000 parts by mass or less, a decrease in the molecular weight of the epoxy group and acid group-containing resin (A) is suppressed by chain transfer action, and the epoxy group and acid group-containing resin (A) The viscosity can be controlled within an appropriate range.
- the blending amount of the solvent to 30 parts by mass or more, an abnormal polymerization reaction can be prevented and the polymerization reaction can be stably performed, and the epoxy group and acid group-containing resin (A) can be colored or gel. Can also be prevented.
- the polymerization initiator that can be used for the production of the epoxy group- and acid group-containing resin (A) is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t- And butyl peroxy-2-ethylhexanoate. These can 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 when the total of the constituent monomers of the epoxy group and acid group-containing resin (A) is 100 parts by mass. ⁇ 10 parts by mass.
- the monomer (a-1), the unsaturated carboxylic acid (a-2), optional components other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) Bulk polymerization may be performed using a radical polymerizable monomer and a polymerization initiator.
- An ethylenic carbon-carbon double bond can be further introduced into the epoxy group- and acid group-containing resin (A) obtained by the above copolymerization reaction.
- the sensitivity and developability of the resin composition are improved.
- a part of the carboxyl group derived from the unsaturated carboxylic acid (a-2) constituting the epoxy group and acid group-containing resin (A), a functional group having reactivity with the carboxyl group, and an ethylenic carbon-carbon double A monomer (a-3) having a bond in one molecule may be added to introduce an ethylenic carbon-carbon double bond.
- the epoxy group- and acid group-containing resin (A) has a functional group that reacts with the carboxyl group and an ethylenic carbon-carbon double bond in part of the carboxyl group derived from the unsaturated carboxylic acid (a-2). It contains a constituent monomer unit having an ethylenic carbon-carbon double bond to which the monomer (a-3) contained in the molecule is added.
- the functional group that reacts with the carboxyl group include an isocyanato group, an epoxy group, and a vinyl ether group. Of these, isocyanato groups are preferred from the viewpoint of reactivity during the addition reaction.
- the same monomers 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.
- 2- (meth) acryloyloxyethyl isocyanate, 1,1- examples thereof include bis (meth) acryloyloxymethyl) ethyl isocyanate and 2- (isocyanatoethyloxy) ethyl (meth) acrylate.
- 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 specific examples include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. .
- the epoxy group- and acid group-containing resin (A) contains an acid anhydride group
- An ethylenic carbon-carbon double bond may be introduced by addition.
- the functional group that reacts with the acid anhydride group include a hydroxyl group.
- the reaction of introducing a carbon-carbon double bond by adding a monomer having a reactive functional group to the carboxyl group, epoxy group or acid anhydride group in the epoxy group- and acid group-containing resin (A), A monomer to be added to the epoxy group- and acid group-containing resin (A), a polymerization inhibitor, and a catalyst are added, and the reaction is preferably performed at 50 to 150 ° C, more preferably at 80 to 130 ° C.
- the addition reaction can be performed without removing the solvent after the completion of the copolymerization reaction.
- a polymerization inhibitor may be added to prevent gelation due to polymerization of the epoxy group- and acid group-containing resin (A).
- a polymerization inhibitor For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned.
- the catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. Can be mentioned.
- the acid value (JIS K6901: 2008 5.3.2) of the epoxy group and acid group-containing resin (A) used in the present invention is not limited, but preferably 10 to 350 mgKOH / g when used for a color filter. More preferably, it is 30 to 200 mgKOH / g, still more preferably 50 to 180 mgKOH / g, and particularly preferably 70 to 150 mgKOH / g.
- the acid value is 10 mgKOH / g or more, sufficient developability can be obtained.
- the acid value is 350 mgKOH / g or less, sufficient developability can be obtained without dissolving the exposed portion (photocured portion) in the alkaline developer.
- the molecular weight of the epoxy group- and acid group-containing resin (A) is preferably 1,000 to 50,000, more preferably. 3000 to 40000.
- the molecular weight is 1000 or more, good sensitivity can be obtained without occurrence of chipping of a colored pattern after development.
- the molecular weight is 50000 or less, the development time is sufficiently short and practical.
- the epoxy group- and acid group-containing resin (A) has an unsaturated group
- the unsaturated group equivalent is not limited, but is preferably 100 to 4000 g / mol, more preferably 200 to 3000 g / mol.
- the unsaturated group equivalent is 100 g / mol or more, it is effective to further improve the heat decomposability and heat yellowing. On the other hand, when the unsaturated group equivalent is 4000 g / mol or less, it is effective to further increase the sensitivity.
- the resin composition of the present invention contains a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate.
- a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate include, for example, pentaerythritol di- or tri (meth) acrylate polybasic acid monoester, dipentaerythritol di-, tri-, tetra- or penta- Specific examples include (meth) acrylate polybasic acid monoesters.
- dipentaerythritol pentaacrylate succinic acid modified product pentaerythritol triacrylate succinic acid modified product
- dipentaerythritol pentaacrylate phthalic acid modified product pentaerythritol
- examples thereof include polybasic acid-modified products in which an acid anhydride is added to the hydroxyl group of a hydroxyl group-containing polyfunctional (meth) acrylate such as a modified product of triacrylate phthalic acid. These can be used alone or in combination of two or more. Among these, from the viewpoint of solvent resistance, a succinic acid-modified product of a hydroxyl group-containing polyfunctional (meth) acrylate is preferable.
- the blending amount of the polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is preferably 10 to 90% by mass, more preferably based on the sum of the components (A) and (B). It is 20 to 80% by mass, and more preferably 25 to 70% by mass. If it is the compounding quantity of this range, it will become a resin composition which has a suitable viscosity, and it has suitable photocurability by mix
- the resin composition of the present invention contains a solvent (C).
- the solvent (C) may be an inert solvent that dissolves the epoxy group- and acid group-containing resin (A) and the polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate and does not react with these. If it does not specifically limit.
- the solvent (C) the same solvent as that used for the copolymerization reaction when producing the epoxy group- and acid group-containing resin (A) can be used, and the solvent contained after the copolymerization reaction is used as it is. You can also. You may add further in the case of preparation of the resin composition of this invention. Or when adding the other component mentioned later, you may use the solvent which coexists with those components as it is.
- the solvent (C) examples 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, tripropylene glycol monomethyl ether, ethylene
- examples include 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 can be used alone or in combination of two or more.
- glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in the copolymerization reaction when producing the epoxy group- and acid group-containing resin (A) are preferable.
- the blending amount of the solvent (C) is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, when the total of the components excluding the solvent (C) in the resin composition of the present invention is 100 parts by mass. Part, more preferably 100 to 700 parts by weight. If it is the compounding quantity of this range, it will become a resin composition which has a suitable viscosity.
- a photopolymerization initiator (D) and a colorant (E) are further blended and used.
- the photopolymerization initiator (D) is not particularly limited.
- benzoin such as benzoin and benzoin methyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone , Acetophenones such as 4- (1-t-butyldioxy-1-methylethyl) acetophenone; alkylphenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone Thioxanthones such as ace
- the blending amount of the photopolymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 when the total of the components (A) and (B) is 100 parts by mass. Parts by mass, more preferably 1 to 15 parts by mass. If it is the compounding quantity of this range, it will become a resin composition which has appropriate photocurability.
- the colorant (E) is not particularly limited as long as it dissolves or disperses in the resin composition of the present invention, and examples thereof include dyes and pigments.
- examples thereof include dyes and pigments.
- sufficient solvent resistance can be obtained even when baking is performed at a relatively low temperature (215 ° C. or lower) as will be described later. is there. Therefore, in the resin composition of the present invention, a colored pattern can be obtained by freely using a wider variety of dyes.
- an acid dye having an acid group such as a carboxyl group an acid dye It is preferable to use a salt with a nitrogen compound or a sulfonamide of an acidic dye.
- dyes examples include: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 33, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow1, 3, 9, 11, 17, 23, 25, 29, 34, 36
- pigments examples include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. CI orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; I.
- Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; I. Green pigments such as C.I. Pigment Green 7, 36, 58; I. Brown pigments such as C.I. Pigment Brown 23 and 25; I. And black pigments such as CI pigment blacks 1 and 7, carbon black, titanium black, and iron oxide. These can be used alone or in combination of two or more depending on the color of the target pixel. Note that the above dyes and pigments may be used in combination depending on the target pixel color.
- the blending amount is preferably 5 to 80 parts by weight with respect to 100 parts by weight of the total of the components excluding the solvent (C) in the resin composition of the present invention.
- the amount is preferably 5 to 70 parts by mass, and more preferably 10 to 60 parts by mass.
- a known dispersant may be blended in the resin composition from the viewpoint of improving the dispersibility of the pigment.
- the dispersant it is preferable to use a polymer dispersant excellent in dispersion stability over time.
- polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. System dispersants and the like.
- EFKA registered trademark, manufactured by Efcar Chemicals Beebuy (BASF)
- Disperbyk registered trademark, manufactured by Big Chemie Japan Co., Ltd.
- Disparon registered trademark, manufactured by Enomoto Kasei Co., Ltd.
- SOLPERSE trademark, the Lubrizol company make
- the photopolymerization initiator (D) and the colorant (E) are preferably blended in an amount of 90 epoxy group and acid group-containing resin (A) with respect to the sum of the components (A) and (B).
- (C) is 30 to 1000 parts by mass, and the sum of the components (A) and (B) is 100 parts by mass
- the photopolymerization initiator (D) is 0.1 to 30 parts by mass
- the solvent ( The sum of the components excluding C) is 100 parts by mass.
- the agent (E) is 5 to 80 parts by mass, and more preferably 80 to 20% by mass of the epoxy group and acid group-containing resin (A) with respect to the sum of the components (A) and (B).
- the solvent (C) is 50 to 50% by mass.
- the photopolymerization initiator (D) is 0.5 to 20 parts by mass
- the components excluding the solvent (C) in the resin composition When the total is 100 parts by mass, the colorant (E) is 5 to 70 parts by mass, and more preferably the epoxy group and acid group-containing resin (A) with respect to the total of the components (A) and (B).
- the amount of tellurium (B) is 25 to 70% by mass and the total of the components excluding the solvent (C) in the resin composition is 100 parts by mass, the solvent (C) is 100 to 700 parts by mass, the component (A) and the component (B)
- the photopolymerization initiator (D) is 1 to 15 parts by mass
- the colorant (E) is 10 ⁇ 60 parts by mass.
- the resin composition of the present invention does not contain a colorant (E), an epoxy group- and acid group-containing resin (A), a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate, a solvent (C ) And the photopolymerization initiator (D) can be applied to the above numerical values.
- the resin composition of the present invention does not contain the photopolymerization initiator (D) and the colorant (E), the epoxy group and acid group-containing resin (A), and the hydroxyl group-containing polyfunctional (meth) acrylate
- the said numerical value is applicable to the compounding quantity of a basic acid monoester (B) and a solvent (C).
- the resin composition of the present invention may contain known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart predetermined characteristics.
- the amount of these additives is not particularly limited as long as it does not impair the effects of the present invention.
- the resin composition of this invention can be manufactured by mixing said component using a well-known mixing apparatus.
- the resin composition of the present invention is a resin composition containing an epoxy group- and acid group-containing resin (A), a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B), and a solvent (C). After the product is prepared, the photopolymerization initiator (D) and an optional colorant (E) can be mixed and produced.
- the resin composition of this invention can be used for formation of the coloring pattern of a color filter, and can also be used for another use.
- the resin composition of the present invention obtained as described above has alkali developability, it can be developed by using an alkaline aqueous solution.
- the resin composition of the present invention is excellent in sensitivity and developability and can give a cured coating film excellent in solvent resistance. Therefore, the resin composition of the present invention is suitable for use as various resists, in particular as a resist used for forming a colored pattern of a color filter incorporated in an organic EL display, a liquid crystal display device, or a solid-state imaging device.
- the resin composition of this invention gives the cured coating film excellent in characteristics, such as solvent resistance, it can also be used for a various coating, an adhesive agent, the binder for printing inks, etc.
- FIG. 1 is a cross-sectional view of a color filter according to an embodiment of the present invention.
- the color filter includes a substrate 1, a black matrix 3 formed on the boundary between the RGB pixels 2 and the pixels 2 formed on the substrate 1, and a protection formed on the pixels 2 and the black matrix 3.
- the membrane 4 In this configuration, other configurations can be used except that at least one of the pixel 2 and the black matrix 3 (colored pattern) is formed using the above resin composition.
- the color filter shown in FIG. 1 is an example, and the present invention is not limited to this configuration.
- a colored pattern is formed on the substrate 1.
- the black matrix 3 and the pixels 2 are sequentially formed on the substrate 1.
- the substrate 1 is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, and the like can be used. .
- the coloring pattern can be formed by using photolithography. Specifically, after applying the above resin composition on the substrate 1 to form a coating film, the coating film is exposed through a photomask having a predetermined pattern, and the exposed portion is photocured. And a predetermined pattern can be formed by developing after baking an unexposed part with aqueous alkali solution, and baking.
- a method for applying the resin composition is not particularly limited, and screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used.
- coating of a resin composition you may volatilize volatile components, such as a solvent (C), by heating using heating means, such as a circulation oven, an infrared heater, and a hotplate, as needed.
- the heating conditions are not particularly limited, and may be set as appropriate according to the type of resin composition to be used. In general, heating may be performed at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.
- the light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Further, the exposure amount is not particularly limited, and may be appropriately adjusted according to the type of the resin composition to be used.
- the aqueous alkali solution used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethylethanolamine; 3 -Methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ - Aqueous solutions of methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate Etc.
- an amine compound such as ethy
- the baking conditions are not particularly limited, and heat treatment may be performed according to the type of the resin composition to be used. However, by using the resin composition of the present invention, baking can be performed at a temperature lower than conventional. Yes, preferably at 215 ° C. or lower, more preferably at 130 to 215 ° C. for 10 to 60 minutes. Since sufficient solvent resistance can be obtained even at a baking temperature lower than before, dyes that could not be used due to the problem of deterioration due to heat can be used in more types.
- a desired coloring pattern can be formed by sequentially repeating the coating, exposure, development and baking as described above using the resin composition for the black matrix 3 and the resin composition for the pixel 2.
- the formation method of the coloring pattern by photocuring was demonstrated above, if the resin composition which mix
- a desired coloring pattern can also be formed by heating after application.
- the protective film 4 is formed on the colored pattern (pixel 2 and black matrix 3).
- the protective film 4 is not particularly limited, and may be formed using a known film.
- the color filter produced in this way is produced using a resin composition that gives a cured coating film with excellent sensitivity and developability and excellent solvent resistance, so a colored pattern with excellent solvent resistance.
- an acid value is an acid value of the epoxy group and acid group containing resin (A) measured according to JISK6901: 2008 5.3.2, Comprising: In 1g of epoxy group and acid group containing resin (A) It means the number of mg of potassium hydroxide required to neutralize the contained acidic component.
- a weight average molecular weight means the standard polystyrene conversion weight average molecular weight measured on condition of the following using gel permeation chromatography (GPC).
- 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 dropping, the mixture was further stirred for 2 hours at 80 ° C. to carry out a copolymerization reaction. 7 resin-containing liquid (solid content acid value 120 mgKOH / g, weight average molecular weight 8000) was obtained. The number of moles of epoxy groups relative to 1 mole of acid groups of the resin in the obtained resin-containing liquid was 2.
- NMP N-methyl-2-pyrrolidone
- the prepared resin composition was spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) at 210 ° C. so that the thickness after baking was 2.5 ⁇ m, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized. Next, the coating film is exposed to light having a wavelength of 365 nm (exposure amount: 300 mJ / cm 2 ), the exposed portion is photocured, and then left in a drier at a baking temperature of 210 ° C. for 20 minutes to produce a cured coating film. did.
- NMP N-methyl-2-pyrrolidone
- the increase in transmittance means that the colorant is eluted into N-methyl-2-pyrrolidone (NMP), and the difference between the initial transmittance and the transmittance after impregnation with N-methyl-2-pyrrolidone (NMP). It can be said that the smaller the amount, the higher the solvent resistance.
- NMP N-methyl-2-pyrrolidone
- the prepared resin composition was spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure was 2.5 ⁇ m, and then heated at 90 ° C. for 3 minutes to volatilize the solvent. I let you.
- a photomask having a predetermined pattern was disposed at a distance of 100 ⁇ m from the coating film, and the coating film was exposed through this photomask (exposure amount 150 mJ / cm 2 ), and the exposed portion was photocured.
- an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C.
- the resin composition of the present invention is suitable as a color filter resist. Furthermore, by using the resin composition of the present invention, a highly reliable color filter having a colored pattern excellent in solvent resistance can be obtained.
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Abstract
Description
また、カラーフィルターの色再現特性を向上させるために、配合する着色剤の含有量を多くしたり、膜厚を厚くするなどの必要があるが、これらは同時に感度の低下、現像性の低下などの問題が生じる傾向にあり、更なる性能向上が求められている(特許文献4)。 Therefore, for example, methods for improving solvent resistance using a copolymer having an epoxy group or oxetanyl group and a carboxyl group or a phenolic hydroxyl group (
In addition, in order to improve the color reproduction characteristics of the color filter, it is necessary to increase the content of the colorant to be blended or to increase the film thickness. However, these simultaneously reduce sensitivity, developability, etc. Therefore, further performance improvement is required (Patent Document 4).
従って、本発明は、上記のような課題を解決するためになされたものであり、感度や現像性が良好であると共に、耐溶剤性に優れた硬化塗膜を与える樹脂組成物を提供することを目的とする。また、本発明は、耐溶剤性に優れた硬化塗膜からなる着色パターンを有するカラーフィルターを提供することを目的とする。 However, the conventional photosensitive resin composition may not have sufficient sensitivity and developability, or a cured coating film having excellent solvent resistance may not be obtained.
Accordingly, the present invention has been made to solve the above-described problems, and provides a resin composition that provides a cured coating film having good sensitivity and developability and excellent solvent resistance. With the goal. Moreover, an object of this invention is to provide the color filter which has a coloring pattern which consists of a cured coating film excellent in solvent resistance.
[1]エポキシ基及び酸基含有樹脂(A)と、水酸基含有多官能(メタ)アクリレートの多塩基酸モノエステル(B)と、溶剤(C)とを含有する樹脂組成物であって、前記エポキシ基及び酸基含有樹脂(A)中の酸基1モルに対して、エポキシ基が0.5~3.0モルであることを特徴とする樹脂組成物。
[2]前記エポキシ基及び酸基含有樹脂(A)の構成モノマー単位として、エチレン性炭素-炭素二重結合とエポキシ基とを一分子中に有するモノマー(a-1)由来のモノマー単位を含有する[1]に記載の樹脂組成物。
[3]前記エポキシ基及び酸基含有樹脂(A)の構成モノマー単位として、不飽和カルボン酸(a-2)由来のモノマー単位を含有する[1]又は[2]に記載の樹脂組成物。
[4]前記エポキシ基及び酸基含有樹脂(A)が、前記不飽和カルボン酸(a-2)由来のカルボキシル基の一部に、カルボキシル基と反応する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマー(a-3)が付加されたエチレン性炭素-炭素二重結合を有する構成モノマー単位を含有する[3]に記載の樹脂組成物。
[5]前記エチレン性炭素-炭素二重結合とエポキシ基とを一分子中に有するモノマー(a-1)が、エポキシ基含有(メタ)アクリレートである[2]に記載の樹脂組成物。
[6]前記カルボキシル基と反応する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマー(a-3)が、エポキシ基含有(メタ)アクリレートおよびイソシアナト基含有(メタ)アクリレートから選択される1種または2種以上である[4]に記載の樹脂組成物。
[7]前記水酸基含有多官能(メタ)アクリレートの多塩基酸モノエステル(B)が、ペンタエリスリトールのジ又はトリ(メタ)アクリレートの多塩基酸モノエステル、ジペンタエリスリトールのジ、トリ、テトラ又はペンタ(メタ)アクリレートの多塩基酸モノエステルからなる群から選ばれる1種または2種以上である[1]~[6]のいずれかに記載の樹脂組成物。
[8]前記エポキシ基及び酸基含有樹脂(A)の酸価が10~350mgKOH/gである[1]~[7]のいずれかに記載の樹脂組成物。
[9]光重合開始剤(D)を更に含有する[1]~[8]のいずれかに記載の樹脂組成物。
[10]着色剤(E)を更に含有する[1]~[9]のいずれかに記載の樹脂組成物。
[11]前記着色剤(E)が、染料及び顔料からなる群から選択される少なくとも1種である[10]に記載の樹脂組成物。
[12][10]又は[11]に記載の樹脂組成物の硬化塗膜からなる着色パターンを有するカラーフィルター。
[13][12]に記載のカラーフィルターを具備する画像表示素子。
[14][10]又は[11]に記載の樹脂組成物を基板上に塗布、露光及びアルカリ水溶液により現像する工程と、215℃以下の温度条件でベーキングし、着色パターンを形成する工程とを含むカラーフィルターの製造方法。 That is, the present invention is shown by the following [1] to [14].
[1] A resin composition comprising an epoxy group- and acid group-containing resin (A), a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate, and a solvent (C), A resin composition characterized in that the epoxy group is 0.5 to 3.0 mol per 1 mol of the acid group in the epoxy group and acid group-containing resin (A).
[2] Containing a monomer unit derived from the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule as constituent monomer units of the epoxy group- and acid group-containing resin (A) The resin composition according to [1].
[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 acid group-containing resin (A).
[4] The epoxy group- and acid group-containing resin (A) is a part of the carboxyl group derived from the unsaturated carboxylic acid (a-2), a functional group that reacts with the carboxyl group, and an ethylenic carbon-carbon double The resin composition according to [3], comprising a constituent monomer unit having an ethylenic carbon-carbon double bond to which a monomer (a-3) having a bond in one molecule is added.
[5] The resin composition according to [2], wherein the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule is an epoxy group-containing (meth) acrylate.
[6] The monomer (a-3) having in one molecule a functional group that reacts with the carboxyl group and an ethylenic carbon-carbon double bond is an epoxy group-containing (meth) acrylate and isocyanato group-containing (meth) acrylate. The resin composition according to [4], which is one or more selected from the group consisting of:
[7] The polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is a dibasic acid monoester of pentaerythritol, a dibasic acid monoester of tri (meth) acrylate, dipentaerythritol di, tri, tetra, or The resin composition according to any one of [1] to [6], which is one or more selected from the group consisting of polybasic acid monoesters of penta (meth) acrylate.
[8] The resin composition according to any one of [1] to [7], wherein the epoxy group- and acid group-containing resin (A) has an acid value of 10 to 350 mgKOH / g.
[9] The resin composition according to any one of [1] to [8], further containing a photopolymerization initiator (D).
[10] The resin composition according to any one of [1] to [9], further containing a colorant (E).
[11] The resin composition according to [10], wherein the colorant (E) is at least one selected from the group consisting of a dye and a pigment.
[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] Applying the resin composition according to [10] or [11] on a substrate, exposing and developing with an alkaline aqueous solution, and baking at a temperature of 215 ° C. or lower to form a colored pattern A method for producing a color filter.
ことができる。 Examples of the solvent that can be used for 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 glycol monobutyl ether, and diethylene glycol monomethyl ether. Hexyl ether, ethylene glycol mono 2-ethylhexyl ether, ethylene glycol monoallyl ether, ethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol mono Chill ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether. These can be used alone or in combination of two or more.
装置:京都電子工業株式会社製、KF水分計 MKA-520
注入量:1mL
滴定液:アクアミクロン(登録商標)滴定剤SS3mg(株式会社エーピーアイコーポレーション製)
電極液:アクアミクロン(登録商標)脱水溶剤PP(株式会社エーピーアイコーポレーション製) Although the moisture content of a solvent is not specifically limited, It is preferable that it is 1 mass% or less. When the water content is 1% by mass or less, an epoxy group- and acid group-containing resin (A) having better solvent resistance can be obtained. The water content of the solvent can be measured by the Karl Fischer method under the following conditions.
Apparatus: Kyoto Electronics Industry Co., Ltd., KF moisture meter MKA-520
Injection volume: 1 mL
Titration solution: Aquamicron (registered trademark) titrant SS3 mg (manufactured by API Corporation)
Electrode solution: Aquamicron (registered trademark) dehydrated solvent PP (manufactured by API Corporation)
なお、有機溶剤を使用せずに、モノマー(a-1)、不飽和カルボン酸(a-2)、任意成分としての、モノマー(a-1)及び不飽和カルボン酸(a-2)以外のラジカル重合可能なモノマー、並びに重合開始剤を使用して塊状重合を行ってもよい。 The blending amount of the polymerization initiator is preferably 0.5 to 20 parts by mass, more preferably 1.0 when the total of the constituent monomers of the epoxy group and acid group-containing resin (A) is 100 parts by mass. ~ 10 parts by mass.
Without using an organic solvent, the monomer (a-1), the unsaturated carboxylic acid (a-2), optional components other than the monomer (a-1) and the unsaturated carboxylic acid (a-2) Bulk polymerization may be performed using a radical polymerizable monomer and a polymerization initiator.
例えば、エポキシ基及び酸基含有樹脂(A)を構成する不飽和カルボン酸(a-2)由来のカルボキシル基の一部に、カルボキシル基と反応性を有する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマー(a-3)を付加してエチレン性炭素-炭素二重結合を導入してもよい。これによりエポキシ基及び酸基含有樹脂(A)は不飽和カルボン酸(a-2)由来のカルボキシル基の一部に、カルボキシル基と反応する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマー(a-3)が付加されたエチレン性炭素-炭素二重結合を有する構成モノマー単位を含有する。カルボキシル基と反応する官能基としては、イソシアナト基、エポキシ基、ビニルエーテル基等が挙げられる。中でも、付加反応の際の反応性の観点からイソシアナト基が好ましい。エポキシ基を有するモノマー(a-3)としては、モノマー(a-1)として例示したものと同様のものを用いることができる。また、イソシアナト基を有するモノマー(a-3)としては、特に限定されないが、イソシアナト基含有(メタ)アクリレートが好ましく、具体的には、2-(メタ)アクリロイルオキシエチルイソシアネート、1,1-(ビス(メタ)アクリロイルオキシメチル)エチルイソシアネート、2-(イソシアナトエチルオキシ)エチル(メタ)アクリレートなどが挙げられる。これらの中でも、イソシアナト基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマーが好ましく、2-(メタ)アクリロイルオキシエチルイソシアネートがより好ましい。ビニルエーテル基を有するモノマー(a-3)としては、特に限定されないが、ビニルエーテル(メタ)アクリレートが好ましく、具体的には、(メタ)アクリル酸2-(2-ビニルオキシエトキシ)エチルなどが挙げられる。
さらに、エポキシ基及び酸基含有樹脂(A)が酸無水物基を含む場合には、酸無水物基と反応する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマーを付加させてエチレン性炭素-炭素二重結合を導入してもよい。酸無水物基と反応する官能基としては、ヒドロキシル基が挙げられる。 An ethylenic carbon-carbon double bond can be further introduced into the epoxy group- and acid group-containing resin (A) obtained by the above copolymerization reaction. Thereby, the sensitivity and developability of the resin composition are improved.
For example, a part of the carboxyl group derived from the unsaturated carboxylic acid (a-2) constituting the epoxy group and acid group-containing resin (A), a functional group having reactivity with the carboxyl group, and an ethylenic carbon-carbon double A monomer (a-3) having a bond in one molecule may be added to introduce an ethylenic carbon-carbon double bond. Thus, the epoxy group- and acid group-containing resin (A) has a functional group that reacts with the carboxyl group and an ethylenic carbon-carbon double bond in part of the carboxyl group derived from the unsaturated carboxylic acid (a-2). It contains a constituent monomer unit having an ethylenic carbon-carbon double bond to which the monomer (a-3) contained in the molecule is added. Examples of the functional group that reacts with the carboxyl group include an isocyanato group, an epoxy group, and a vinyl ether group. Of these, isocyanato groups are preferred from the viewpoint of reactivity during the addition reaction. As the monomer (a-3) having an epoxy group, the same monomers as those exemplified as the monomer (a-1) can be used. Further, the monomer (a-3) having an isocyanato group is not particularly limited, but isocyanato group-containing (meth) acrylate is preferable. Specifically, 2- (meth) acryloyloxyethyl isocyanate, 1,1- ( Examples thereof include bis (meth) acryloyloxymethyl) ethyl isocyanate and 2- (isocyanatoethyloxy) ethyl (meth) acrylate. Among these, 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 specific examples include 2- (2-vinyloxyethoxy) ethyl (meth) acrylate. .
Further, when the epoxy group- and acid group-containing resin (A) contains an acid anhydride group, a monomer having a functional group that reacts with the acid anhydride group and an ethylenic carbon-carbon double bond in one molecule. An ethylenic carbon-carbon double bond may be introduced by addition. Examples of the functional group that reacts with the acid anhydride group include a hydroxyl group.
ここで、重合禁止剤を、エポキシ基及び酸基含有樹脂(A)の重合によるゲル化を防ぐために添加してもよい。重合禁止剤としては、特に限定されないが、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテルなどが挙げられる。また、触媒としては、特に限定されないが、例えば、トリエチルアミンのような第3級アミン、トリエチルベンジルアンモニウムクロライドのような第4級アンモニウム塩、トリフェニルホスフィンのようなリン化合物、クロムのキレート化合物などが挙げられる。 The reaction of introducing a carbon-carbon double bond by adding a monomer having a reactive functional group to the carboxyl group, epoxy group or acid anhydride group in the epoxy group- and acid group-containing resin (A), A monomer to be added to the epoxy group- and acid group-containing resin (A), a polymerization inhibitor, and a catalyst are added, and the reaction is preferably performed at 50 to 150 ° C, more preferably at 80 to 130 ° C. In this addition reaction, there is no particular problem even if the solvent used in the copolymerization reaction is included. Therefore, the addition reaction can be performed without removing the solvent after the completion of the copolymerization reaction.
Here, a polymerization inhibitor may be added to prevent gelation due to polymerization of the epoxy group- and acid group-containing resin (A). Although it does not specifically limit as a polymerization inhibitor, For example, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, etc. are mentioned. The catalyst is not particularly limited, and examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chelate compounds of chromium. Can be mentioned.
また、エポキシ基及び酸基含有樹脂(A)の分子量(後述のゲルパーミエーションクロマトグラフィー(GPC)を用いて測定したポリスチレン換算の重量平均分子量)は、好ましくは1000~50000であり、より好ましくは3000~40000である。この分子量が1000以上であると、現像後に着色パターンの欠けが発生することなく、良好な感度が得られる。一方、この分子量が50000以下であると、現像時間が十分に短く実用的である。
また、エポキシ基及び酸基含有樹脂(A)が不飽和基を有する場合、その不飽和基当量の制限はないが、好ましくは100~4000g/molであり、より好ましくは200~3000g/molである。この不飽和基当量が100g/mol以上であると、耐熱分解性、及び耐熱黄変性をより高めるには効果的である。一方、この不飽和基当量が4000g/mol以下であると、感度をより高めるには効果的である。 The acid value (JIS K6901: 2008 5.3.2) of the epoxy group and acid group-containing resin (A) used in the present invention is not limited, but preferably 10 to 350 mgKOH / g when used for a color filter. More preferably, it is 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 can be obtained. On the other hand, when the acid value is 350 mgKOH / g or less, sufficient developability can be obtained without dissolving the exposed portion (photocured portion) in the alkaline developer.
The molecular weight of the epoxy group- and acid group-containing resin (A) (polystyrene-converted weight average molecular weight measured using gel permeation chromatography (GPC) described later) is preferably 1,000 to 50,000, more preferably. 3000 to 40000. When the molecular weight is 1000 or more, good sensitivity can be obtained without occurrence of chipping of a colored pattern after development. On the other hand, when the molecular weight is 50000 or less, the development time is sufficiently short and practical.
In addition, when the epoxy group- and acid group-containing resin (A) has an unsaturated group, the unsaturated group equivalent is not limited, but is preferably 100 to 4000 g / mol, more preferably 200 to 3000 g / mol. is there. When the unsaturated group equivalent is 100 g / mol or more, it is effective to further improve the heat decomposability and heat yellowing. On the other hand, when the unsaturated group equivalent is 4000 g / mol or less, it is effective to further increase the sensitivity.
溶剤(C)としては、エポキシ基及び酸基含有樹脂(A)を製造する際の共重合反応に用いた溶剤と同じものを用いることができ、共重合反応後に含まれている溶剤をそのまま用いることもできる。本発明の樹脂組成物の調製の際に更に加えてもよい。あるいは、後述するその他の成分を加える際に、それらの成分と共存する溶剤をそのまま用いてもよい。溶剤(C)の具体例としては、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、酢酸エチル、酢酸ブチル、酢酸イソプロピル、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテートなどが挙げられる。これらは、単独で又は2種以上を組み合わせて用いることができる。また、これらの中でも、エポキシ基及び酸基含有樹脂(A)を製造する際の共重合反応において使用されるプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテートなどのグリコールエーテル系溶剤が好ましい。 The resin composition of the present invention contains a solvent (C). The solvent (C) may be an inert solvent that dissolves the epoxy group- and acid group-containing resin (A) and the polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate and does not react with these. If it does not specifically limit.
As the solvent (C), the same solvent as that used for the copolymerization reaction when producing the epoxy group- and acid group-containing resin (A) can be used, and the solvent contained after the copolymerization reaction is used as it is. You can also. You may add further in the case of preparation of the resin composition of this invention. Or when adding the other component mentioned later, you may use the solvent which coexists with those components 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, tripropylene glycol monomethyl ether, ethylene Examples include 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 can be used alone or in combination of two or more. Among these, glycol ether solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate used in the copolymerization reaction when producing the epoxy group- and acid group-containing resin (A) are preferable.
特に、本発明の樹脂組成物では、後述するように比較的低い温度(215℃以下)でベーキングを行っても十分な耐溶剤性が得られるので、熱による染料の劣化が生じ難いという利点がある。そのため、本発明の樹脂組成物では、より多種類の染料を自由に用いて着色パターンを得ることができる。 The colorant (E) is not particularly limited as long as it dissolves or disperses in the resin composition of the present invention, and examples thereof include dyes and pigments.
In particular, in the resin composition of the present invention, sufficient solvent resistance can be obtained even when baking is performed at a relatively low temperature (215 ° C. or lower) as will be described later. is there. Therefore, in the resin composition of the present invention, a colored pattern can be obtained by freely using a wider variety of dyes.
なお、目的とする画素の色に応じて、上記の染料及び顔料を組み合わせて用いることもできる。 Examples of pigments include C.I. I.
Note that the above dyes and pigments may be used in combination depending on the target pixel color.
分散剤の配合量は、使用する顔料などの種類に応じて適宜設定すればよい。 When a pigment is used as the colorant (E), a known dispersant may be blended in the resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant excellent in dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. System dispersants and the like. As such a polymer dispersant, EFKA (registered trademark, manufactured by Efcar Chemicals Beebuy (BASF)), Disperbyk (registered trademark, manufactured by Big Chemie Japan Co., Ltd.), Disparon (registered trademark, manufactured by Enomoto Kasei Co., Ltd.), You may use what is marketed by brand names, such as SOLPERSE (trademark, the Lubrizol company make).
What is necessary is just to set the compounding quantity of a dispersing agent suitably according to kinds, such as a pigment to be used.
同様に、本発明の樹脂組成物が光重合開始剤(D)及び着色剤(E)を含まない場合でも、エポキシ基及び酸基含有樹脂(A)、水酸基含有多官能(メタ)アクリレートの多塩基酸モノエステル(B)及び溶剤(C)の配合量は、上記数値が適用可能である。 Even when the resin composition of the present invention does not contain a colorant (E), an epoxy group- and acid group-containing resin (A), a polybasic acid monoester (B) of a hydroxyl group-containing polyfunctional (meth) acrylate, a solvent (C ) And the photopolymerization initiator (D) can be applied to the above numerical values.
Similarly, even when the resin composition of the present invention does not contain the photopolymerization initiator (D) and the colorant (E), the epoxy group and acid group-containing resin (A), and the hydroxyl group-containing polyfunctional (meth) acrylate The said numerical value is applicable to the compounding quantity of a basic acid monoester (B) and a solvent (C).
なお、本発明の樹脂組成物は、先にエポキシ基及び酸基含有樹脂(A)、水酸基含有多官能(メタ)アクリレートの多塩基酸モノエステル(B)及び溶剤(C)を含有する樹脂組成物を調製した後、光重合開始剤(D)及び任意の着色剤(E)を混合して製造することも可能である。なお、本発明の樹脂組成物は、カラーフィルターの着色パターンの形成に用いることができる他、他の用途で使用することも可能である。 The resin composition of this invention can be manufactured by mixing said component using a well-known mixing apparatus.
The resin composition of the present invention is a resin composition containing an epoxy group- and acid group-containing resin (A), a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B), and a solvent (C). After the product is prepared, the photopolymerization initiator (D) and an optional colorant (E) can be mixed and produced. In addition, the resin composition of this invention can be used for formation of the coloring pattern of a color filter, and can also be used for another use.
以下、本発明の一実施形態のカラーフィルターについて、図面を用いて説明する。
図1は、本発明の実施の一形態のカラーフィルターの断面図である。図1において、カラーフィルターは、基板1と、基板1上に形成される、RGBの画素2及び画素2の境界に形成されるブラックマトリックス3と、画素2及びブラックマトリックス3上に形成される保護膜4とから構成される。この構成において、画素2及びブラックマトリックス3(着色パターン)の少なくとも一つが上記の樹脂組成物を用いて形成されることを除けば、その他の構成は公知のものを採用することができる。なお、図1に示したカラーフィルターは一例であり、この構成のみに限定されない。 Next, the color filter manufactured using the resin composition of this invention is demonstrated. The color filter of the present invention has a colored pattern obtained from the above resin composition.
Hereinafter, a color filter according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of a color filter according to an embodiment of the present invention. In FIG. 1, the color filter includes a
まず、基板1上に着色パターンを形成する。具体的には、基板1上に、ブラックマトリックス3及び画素2を順次形成する。ここで、基板1としては、特に限定されないが、ガラス基板、シリコン基板、ポリカーボネート基板、ポリエステル基板、ポリアミド基板、ポリアミドイミド基板、ポリイミド基板、アルミニウム基板、プリント配線基板、アレイ基板などを用いることができる。 Next, the manufacturing method of the color filter of one Embodiment of this invention is demonstrated.
First, a colored pattern is formed on the
樹脂組成物の塗布方法としては、特に限定されないが、スクリーン印刷法、ロールコート法、カーテンコート法、スプレーコート法、スピンコート法などを用いることができる。また、樹脂組成物の塗布後、必要に応じて、循環式オーブン、赤外線ヒーター、ホットプレートなどの加熱手段を用いて加熱することにより溶剤(C)などの揮発成分を揮発させてもよい。加熱条件は、特に限定されず、使用する樹脂組成物の種類に応じて適宜設定すればよい。一般には、50℃~120℃の温度で30秒~30分加熱すればよい。 The coloring pattern can be formed by using photolithography. Specifically, after applying the above resin composition on the
A method for applying the resin composition is not particularly limited, and screen printing, roll coating, curtain coating, spray coating, spin coating, and the like can be used. Moreover, after application | coating of a resin composition, you may volatilize volatile components, such as a solvent (C), by heating using heating means, such as a circulation oven, an infrared heater, and a hotplate, as needed. The heating conditions are not particularly limited, and may be set as appropriate according to the type of resin composition to be used. In general, heating may be performed at a temperature of 50 ° C. to 120 ° C. for 30 seconds to 30 minutes.
現像に用いられるアルカリ水溶液としては、特に限定されないが、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、水酸化ナトリウム、水酸化カリウムなどの水溶液;エチルアミン、ジエチルアミン、ジメチルエタノールアミンなどのアミン系化合物の水溶液;3-メチル-4-アミノ-N,N-ジエチルアニリン、3-メチル-4-アミノ-N-エチル-N-β-ヒドロキシエチルアニリン、3-メチル-4-アミノ-N-エチル-N-β-メタンスルホンアミドエチルアニリン、3-メチル-4-アミノ-N-エチル-N-β-メトキシエチルアニリン及びこれらの硫酸塩、塩酸塩又はp-トルエンスルホン酸塩などのp-フェニレンジアミン系化合物の水溶液などを用いることができる。これらの中でも、p-フェニレンジアミン系化合物の水溶液を用いることが好ましい。なお、これらの水溶液には、必要に応じて消泡剤や界面活性剤を添加してもよい。また、上記のアルカリ水溶液による現像の後、水洗して乾燥させることが好ましい。
ベーキングの条件は、特に限定されず、使用する樹脂組成物の種類に応じて加熱処理を行えばよいが、本発明の樹脂組成物を用いることにより、従来よりも低温でベーキングすることが可能であり、好ましくは215℃以下、より好ましくは130~215℃で10~60分間加熱すればよい。従来よりも低いベーキング温度でも十分な耐溶剤性が得られるため、熱による劣化の問題から使用することができなかった染料についても、より多くの種類での使用が可能である。 The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Further, the exposure amount is not particularly limited, and may be appropriately adjusted according to the type of the resin composition to be used.
The aqueous alkali solution used for development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc .; an aqueous solution of an amine compound such as ethylamine, diethylamine, dimethylethanolamine; 3 -Methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β- Aqueous solutions of methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate Etc. can be used. Among these, it is preferable to use an aqueous solution of a p-phenylenediamine compound. In addition, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash and dry after development with the above-mentioned alkaline aqueous solution.
The baking conditions are not particularly limited, and heat treatment may be performed according to the type of the resin composition to be used. However, by using the resin composition of the present invention, baking can be performed at a temperature lower than conventional. Yes, preferably at 215 ° C. or lower, more preferably at 130 to 215 ° C. for 10 to 60 minutes. Since sufficient solvent resistance can be obtained even at a baking temperature lower than before, dyes that could not be used due to the problem of deterioration due to heat can be used in more types.
なお、上記では、光硬化による着色パターンの形成方法を説明したが、光重合開始剤(D)の代わりに、硬化促進剤及び公知のエポキシ樹脂を配合した樹脂組成物を用いれば、インクジェット法により塗布した後、加熱することにより、所望の着色パターンを形成することもできる。
次に、着色パターン(画素2及びブラックマトリックス3)上に保護膜4を形成する。保護膜4としては、特に限定されず、公知のものを用いて形成すればよい。 A desired coloring pattern can be formed by sequentially repeating the coating, exposure, development and baking as described above using the resin composition for the
In addition, although the formation method of the coloring pattern by photocuring was demonstrated above, if the resin composition which mix | blended the hardening accelerator and the well-known epoxy resin was used instead of the photoinitiator (D), it will be by inkjet method. A desired coloring pattern can also be formed by heating after application.
Next, the
カラム:ショウデックス(登録商標) LF-804+LF-804(昭和電工株式会社製)
カラム温度:40℃
試料:樹脂の0.2%テトラヒドロフラン溶液
展開溶媒:テトラヒドロフラン
検出器:示差屈折計(ショウデックス(登録商標) RI-71S)(昭和電工株式会社製)
流速:1mL/min EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In this example, all parts and percentages are based on mass unless otherwise specified. Moreover, an acid value is an acid value of the epoxy group and acid group containing resin (A) measured according to JISK6901: 2008 5.3.2, Comprising: In 1g of epoxy group and acid group containing resin (A) It means the number of mg of potassium hydroxide required to neutralize the contained acidic component. Moreover, a weight average molecular weight means the standard polystyrene conversion weight average molecular weight measured on condition of the following using gel permeation chromatography (GPC).
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Sample: 0.2% tetrahydrofuran solution of resin Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showex (registered trademark) RI-71S) (manufactured by Showa Denko KK)
Flow rate: 1 mL / min
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、324質量部のプロピレングリコールモノメチルエーテルアセテートを入れ、窒素ガス置換しながら攪拌し、80℃に昇温した。次いで、メタクリル酸86質量部(1モル)及びグリシジルメタクリレート71質量部(0.5モル)からなるモノマー混合物に、17質量部の2,2-アゾビス(2,4-ジメチルバレロニトリル)(重合開始剤、和光純薬工業株式会社製V-65)を添加したものを、滴下ロートから2時間にわたってフラスコ中に滴下した。滴下終了後、80℃でさらに2時間攪拌して共重合反応を行い、No.1の樹脂含有液(固形分酸価320mgKOH/g、重量平均分子量10000)を得た。なお、得られた樹脂含有液中の樹脂の酸基1モルに対するエポキシ基のモル数は0.5であった。 <Synthesis Example 1>
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 324 parts by mass of propylene glycol monomethyl ether acetate was added, stirred while replacing with nitrogen gas, and heated to 80 ° C. Next, 17 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) (polymerization start) was added to a monomer mixture consisting of 86 parts by mass (1 mol) of methacrylic acid and 71 parts by mass (0.5 mol) of glycidyl methacrylate. An agent, V-65 manufactured by Wako Pure Chemical Industries, Ltd., was added dropwise into the flask over 2 hours from the dropping funnel. After completion of the dropping, the mixture was further stirred for 2 hours at 80 ° C. to carry out a copolymerization reaction. 1 resin-containing liquid (solid content acid value 320 mgKOH / g, weight average molecular weight 10,000) was obtained. In addition, the number-of-moles of the epoxy group with respect to 1 mol of acid groups of resin in the obtained resin containing liquid were 0.5.
表1に示すようにプロピレングリコールモノメチルエーテルアセテート(PGMEA)、メタクリル酸(MAa)及びグリシジルメタクリレート(GMA)の使用量を変えたこと以外は、合成例1と同様にして、No.2~5の樹脂含有液を得た。 <Synthesis Examples 2 to 5>
As shown in Table 1, in the same manner as in Synthesis Example 1 except that the amounts of propylene glycol monomethyl ether acetate (PGMEA), methacrylic acid (MAa) and glycidyl methacrylate (GMA) were changed, 2 to 5 resin-containing liquids were obtained.
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、470質量部のプロピレングリコールモノメチルエーテルアセテートを入れ、窒素ガス置換しながら攪拌し、80℃に昇温した。次いで、メタクリル酸86質量部(1モル)及びグリシジルメタクリレート142質量部(1モル)からなるモノマー混合物に、25質量部の2,2-アゾビス(2,4-ジメチルバレロニトリル)(重合開始剤、和光純薬工業株式会社製V-65)を添加したものを、滴下ロートから2時間にわたってフラスコ中に滴下した。滴下終了後、80℃でさらに2時間攪拌して共重合反応を行った。
その後、60℃で0.1質量部のジブチルスズラウレート(触媒、和光純薬工業株式会社製)及び2-イソシアナトエチルメタクリレート(昭和電工株式会社製)78質量部(0.5モル)をフラスコに投入し、1時間撹拌し、その後、160質量部のプロピレングリコールモノメチルエーテルアセテートを投入し、No.6の樹脂含有液(固形分酸価85mgKOH/g、重量平均分子量13000)を得た。なお、得られた樹脂含有液中の樹脂の酸基1モルに対するエポキシ基のモル数は2であった。 <Synthesis Example 6>
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 470 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing with nitrogen gas, and the temperature was raised to 80 ° C. Next, 25 parts by mass of 2,2-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) was added to a monomer mixture consisting of 86 parts by mass (1 mol) of methacrylic acid and 142 parts by mass (1 mol) of glycidyl methacrylate. What added V-65) manufactured by Wako Pure Chemical Industries, Ltd. was dropped into the flask from the dropping funnel over 2 hours. After completion of dropping, the mixture was further stirred at 80 ° C. for 2 hours to carry out a copolymerization reaction.
Thereafter, 0.1 parts by mass of dibutyltin laurate (catalyst, manufactured by Wako Pure Chemical Industries, Ltd.) and 78 parts by mass (0.5 mol) of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko) at 60 ° C. were flasked. And stirred for 1 hour, and then 160 parts by mass of propylene glycol monomethyl ether acetate was added. 6 resin-containing liquid (solid content acid value 85 mgKOH / g, weight average molecular weight 13000) was obtained. The number of moles of epoxy groups relative to 1 mole of acid groups of the resin in the obtained resin-containing liquid was 2.
攪拌装置、滴下ロート、コンデンサー、温度計及びガス導入管を備えたフラスコに、977質量部のプロピレングリコールモノメチルエーテルアセテートを入れ、窒素ガス置換しながら攪拌し、80℃に昇温した。次いで、メタクリル酸86質量部(1モル)、スチレン104質量部(1モル)及びグリシジルメタクリレート284質量部(2モル)からなるモノマー混合物に、52質量部の2,2-アゾビス(2,4-ジメチルバレロニトリル)(重合開始剤、和光純薬工業株式会社製V-65)を添加したものを、滴下ロートから2時間にわたってフラスコ中に滴下した。滴下終了後、80℃でさらに2時間攪拌して共重合反応を行い、No.7の樹脂含有液(固形分酸価120mgKOH/g、重量平均分子量8000)を得た。なお、得られた樹脂含有液中の樹脂の酸基1モルに対するエポキシ基のモル数は2であった。 <Synthesis Example 7>
Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 977 parts by mass of propylene glycol monomethyl ether acetate was added and stirred while replacing with nitrogen gas, and the temperature was raised to 80 ° C. Subsequently, 52 parts by mass of 2,2-azobis (2,4-methylazol) was added to a monomer mixture comprising 86 parts by mass (1 mol) of methacrylic acid, 104 parts by mass (1 mol) of styrene and 284 parts by mass (2 mol) of glycidyl methacrylate. 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 dropping, the mixture was further stirred for 2 hours at 80 ° C. to carry out a copolymerization reaction. 7 resin-containing liquid (solid content acid value 120 mgKOH / g, weight average molecular weight 8000) was obtained. The number of moles of epoxy groups relative to 1 mole of acid groups of the resin in the obtained resin-containing liquid was 2.
表2に示す配合を基本配合とし、樹脂含有液及び重合性モノマーの種類を表3及び4に示すように変更し、実施例1~10及び比較例1~7の樹脂組成物を調製した。 <Preparation of resin composition>
The resin compositions of Examples 1 to 10 and Comparative Examples 1 to 7 were prepared using the composition shown in Table 2 as a basic composition and changing the types of the resin-containing liquid and the polymerizable monomer as shown in Tables 3 and 4.
カラーフィルターの保護膜形成工程で一般に使用される溶剤であるN-メチル-2-ピロリドン(NMP)に対する耐溶剤性の評価を行った。
5cm角ガラス基板(無アルカリガラス基板)上に、調製された樹脂組成物を、210℃でベーキング後の厚さが2.5μmとなるようにスピンコートした後、90℃で3分間加熱して溶剤を揮発させた。次に、塗布膜に波長365nmの光で露光し(露光量300mJ/cm2)、露光部分を光硬化させたのち、ベーキング温度210℃の乾燥器中に20分放置して硬化塗膜を作製した。分光光度計UV-1650PC(株式会社島津製作所製)を用いて、硬化塗膜付き試験片の波長675nmにおける透過率を測定した。次いで、蓋付きシャーレに55質量部のN-メチル-2-ピロリドン(NMP)を入れ、その中に硬化塗膜付き試験片を浸漬した後、60℃で30分経過後の透過率を測定した。結果を表5に示す。透過率の上昇は着色剤がN-メチル-2-ピロリドン(NMP)へ溶出していることを意味しており、初期透過率とN-メチル-2-ピロリドン(NMP)含浸後透過率の差が少ない方が耐溶剤性が高いと言える。 <Evaluation of solvent resistance>
The solvent resistance of N-methyl-2-pyrrolidone (NMP), which is a solvent generally used in the color filter protective film forming step, was evaluated.
The prepared resin composition was spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) at 210 ° C. so that the thickness after baking was 2.5 μm, and then heated at 90 ° C. for 3 minutes. The solvent was volatilized. Next, the coating film is exposed to light having a wavelength of 365 nm (exposure amount: 300 mJ / cm 2 ), the exposed portion is photocured, and then left in a drier at a baking temperature of 210 ° C. for 20 minutes to produce a cured coating film. did. Using a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation), the transmittance of a test piece with a cured coating film at a wavelength of 675 nm was measured. Next, 55 parts by mass of N-methyl-2-pyrrolidone (NMP) was placed in a petri dish with a lid, a test piece with a cured coating film was immersed therein, and the transmittance after 30 minutes at 60 ° C. was measured. . The results are shown in Table 5. The increase in transmittance means that the colorant is eluted into N-methyl-2-pyrrolidone (NMP), and the difference between the initial transmittance and the transmittance after impregnation with N-methyl-2-pyrrolidone (NMP). It can be said that the smaller the amount, the higher the solvent resistance.
5cm角ガラス基板(無アルカリガラス基板)上に、調製された樹脂組成物を、露光後の厚さが2.5μmとなるようにスピンコートした後、90℃で3分間加熱し、溶剤を揮発させた。次に、塗布膜から100μmの距離に所定のパターンのフォトマスクを配置し、このフォトマスクを介して塗布膜を露光(露光量150mJ/cm2)し、露光部分を光硬化させた。次に、0.1質量%の炭酸ナトリウムを含む水溶液を23℃の温度及び0.3MPaの圧力でスプレーすることによって未露光部分を溶解して現像した後、210℃で30分間ベーキングすることで所定のパターンを形成し、アルカリ現像後の残渣を確認した。アルカリ現像後の残渣は、アルカリ現像後のパターンを、(株)日立ハイテクノロジーズ製電子顕微鏡S-3400を用いて観察することにより確認した。この評価の基準は以下の通りである。結果を表5に示す。
○:残渣なし
×:残渣あり <Evaluation of alkali developability>
The prepared resin composition was spin-coated on a 5 cm square glass substrate (non-alkali glass substrate) so that the thickness after exposure was 2.5 μm, and then heated at 90 ° C. for 3 minutes to volatilize the solvent. I let you. Next, a photomask having a predetermined pattern was disposed at a distance of 100 μm from the coating film, and the coating film was exposed through this photomask (exposure amount 150 mJ / cm 2 ), and the exposed portion was photocured. Next, by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23 ° C. and a pressure of 0.3 MPa, the unexposed portion is dissolved and developed, followed by baking at 210 ° C. for 30 minutes. A predetermined pattern was formed, and the residue after alkali development was confirmed. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows. The results are shown in Table 5.
○: No residue ×: Residue
上記のスプレーを用いたアルカリ現像を30秒間行い、アルカリ現像前後におけるパターン厚さの減少量を触針式段差計ET4000M(小坂研究所製)にて測定することにより、感度の良否を判定した。このパターン厚さは、減少量が少ないほど感度が良好であると言えるため、この評価の基準は以下の通りとした。結果を表5に示す。
○:0.20μm未満
×:0.20μm以上 <Evaluation of sensitivity>
The alkali development using the above 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 stylus-type step gauge ET4000M (manufactured by Kosaka Laboratory) to determine the quality of the sensitivity. Since it can be said that the sensitivity of this pattern thickness is better as the amount of decrease is smaller, the criteria for this evaluation were as follows. The results are shown in Table 5.
○: Less than 0.20 μm ×: 0.20 μm or more
Claims (14)
- エポキシ基及び酸基含有樹脂(A)と、水酸基含有多官能(メタ)アクリレートの多塩基酸モノエステル(B)と、溶剤(C)とを含有する樹脂組成物であって、前記エポキシ基及び酸基含有樹脂(A)中の酸基1モルに対して、エポキシ基が0.5~3.0モルであることを特徴とする樹脂組成物。 A resin composition containing an epoxy group and acid group-containing resin (A), a hydroxyl group-containing polyfunctional (meth) acrylate polybasic acid monoester (B), and a solvent (C), the epoxy group and A resin composition characterized in that an epoxy group is 0.5 to 3.0 mol per 1 mol of an acid group in the acid group-containing resin (A).
- 前記エポキシ基及び酸基含有樹脂(A)の構成モノマー単位として、エチレン性炭素-炭素二重結合とエポキシ基とを一分子中に有するモノマー(a-1)由来のモノマー単位を含有する請求項1に記載の樹脂組成物。 The monomer unit derived from the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule as constituent monomer units of the epoxy group- and acid group-containing resin (A). 2. The resin composition according to 1.
- 前記エポキシ基及び酸基含有樹脂(A)の構成モノマー単位として、不飽和カルボン酸(a-2)由来のモノマー単位を含有する請求項1又は2に記載の樹脂組成物。 The resin composition according to claim 1 or 2, comprising a monomer unit derived from an unsaturated carboxylic acid (a-2) as a constituent monomer unit of the epoxy group- and acid group-containing resin (A).
- 前記エポキシ基及び酸基含有樹脂(A)が、前記不飽和カルボン酸(a-2)由来のカルボキシル基の一部に、カルボキシル基と反応する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマー(a-3)が付加されたエチレン性炭素-炭素二重結合を有する構成モノマー単位を含有する請求項3に記載の樹脂組成物。 The epoxy group- and acid group-containing resin (A) has a functional group that reacts with a carboxyl group and an ethylenic carbon-carbon double bond in part of the carboxyl group derived from the unsaturated carboxylic acid (a-2). The resin composition according to claim 3, comprising a constituent monomer unit having an ethylenic carbon-carbon double bond to which the monomer (a-3) contained in one molecule is added.
- 前記エチレン性炭素-炭素二重結合とエポキシ基とを一分子中に有するモノマー(a-1)が、エポキシ基含有(メタ)アクリレートである請求項2に記載の樹脂組成物。 3. The resin composition according to claim 2, wherein the monomer (a-1) having an ethylenic carbon-carbon double bond and an epoxy group in one molecule is an epoxy group-containing (meth) acrylate.
- 前記カルボキシル基と反応する官能基とエチレン性炭素-炭素二重結合とを一分子中に有するモノマー(a-3)が、エポキシ基含有(メタ)アクリレートおよびイソシアナト基含有(メタ)アクリレートから選択される1種または2種以上である請求項4に記載の樹脂組成物。 The monomer (a-3) having a functional group that reacts with the carboxyl group and an ethylenic carbon-carbon double bond in one molecule is selected from an epoxy group-containing (meth) acrylate and an isocyanato group-containing (meth) acrylate. The resin composition according to claim 4, which is one kind or two or more kinds.
- 前記水酸基含有多官能(メタ)アクリレートの多塩基酸モノエステル(B)が、ペンタエリスリトールのジ又はトリ(メタ)アクリレートの多塩基酸モノエステル、ジペンタエリスリトールのジ、トリ、テトラ又はペンタ(メタ)アクリレートの多塩基酸モノエステルからなる群から選ばれる1種または2種以上である請求項1~6のいずれか一項に記載の樹脂組成物。 The polybasic acid monoester (B) of the hydroxyl group-containing polyfunctional (meth) acrylate is a dibasic acid monoester of pentaerythritol di- or tri (meth) acrylate, dipentaerythritol di-, tri-, tetra- or penta- (meta). 7. The resin composition according to claim 1, wherein the resin composition is one or more selected from the group consisting of polybasic acid monoesters of acrylates.
- 前記エポキシ基及び酸基含有樹脂(A)の酸価が10~350mgKOH/gである請求項1~7のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, wherein the epoxy group- and acid group-containing resin (A) has an acid value of 10 to 350 mgKOH / g.
- 光重合開始剤(D)を更に含有する請求項1~8のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 8, further comprising a photopolymerization initiator (D).
- 着色剤(E)を更に含有する請求項1~9のいずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 9, further comprising a colorant (E).
- 前記着色剤(E)が、染料及び顔料からなる群から選択される少なくとも1種である請求項10に記載の樹脂組成物。 The resin composition according to claim 10, wherein the colorant (E) is at least one selected from the group consisting of dyes and pigments.
- 請求項10又は11に記載の樹脂組成物の硬化塗膜からなる着色パターンを有するカラーフィルター。 A color filter having a colored pattern comprising a cured coating film of the resin composition according to claim 10 or 11.
- 請求項12に記載のカラーフィルターを具備する画像表示素子。 An image display device comprising the color filter according to claim 12.
- 請求項10又は11に記載の樹脂組成物を基板上に塗布、露光及びアルカリ水溶液により現像する工程と、
215℃以下の温度条件でベーキングし、着色パターンを形成する工程と
を含むカラーフィルターの製造方法。 Applying the resin composition according to claim 10 or 11 on a substrate, exposure and development with an alkaline aqueous solution;
And a step of baking at a temperature of 215 ° C. or lower to form a colored pattern.
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CN110297394A (en) * | 2018-03-22 | 2019-10-01 | 东友精细化工有限公司 | Photosensitive composition, colour filter and image display device |
CN110297394B (en) * | 2018-03-22 | 2023-09-08 | 东友精细化工有限公司 | Colored photosensitive resin composition, color filter and image display device |
KR20230071160A (en) | 2020-09-23 | 2023-05-23 | 스미또모 베이크라이트 가부시키가이샤 | Polymers, polymer solutions and photosensitive resin compositions |
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TW201631396A (en) | 2016-09-01 |
KR101918433B1 (en) | 2018-11-13 |
CN107108769A (en) | 2017-08-29 |
TWI600970B (en) | 2017-10-01 |
KR20170097757A (en) | 2017-08-28 |
CN107108769B (en) | 2019-02-19 |
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