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WO2022091905A1 - Method for producing carboxy-group-containing resin-containing solution and method for stabilizing carboxy-group-containing resin - Google Patents

Method for producing carboxy-group-containing resin-containing solution and method for stabilizing carboxy-group-containing resin Download PDF

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Publication number
WO2022091905A1
WO2022091905A1 PCT/JP2021/038749 JP2021038749W WO2022091905A1 WO 2022091905 A1 WO2022091905 A1 WO 2022091905A1 JP 2021038749 W JP2021038749 W JP 2021038749W WO 2022091905 A1 WO2022091905 A1 WO 2022091905A1
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WIPO (PCT)
Prior art keywords
carboxy group
group
resin
containing resin
mass
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Application number
PCT/JP2021/038749
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French (fr)
Japanese (ja)
Inventor
和裕 中谷
克浩 小川
篤 古端
貴裕 宮崎
Original Assignee
三菱ケミカル株式会社
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Filing date
Publication date
Application filed by 三菱ケミカル株式会社 filed Critical 三菱ケミカル株式会社
Priority to JP2022559054A priority Critical patent/JPWO2022091905A1/ja
Priority to KR1020237009742A priority patent/KR20230098142A/en
Priority to CN202180069214.2A priority patent/CN116323728A/en
Publication of WO2022091905A1 publication Critical patent/WO2022091905A1/en

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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
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • 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
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • the present invention relates to a method for producing a carboxy group-containing resin-containing liquid, a method for producing ink, a method for producing a photosensitive resin composition, a method for producing a cured product, a method for producing a black matrix, and a method for producing an image display device.
  • a color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially grids and stripes pixels of three or more different colors such as red, green, and blue. It is formed by a pattern such as a shape or a mosaic shape.
  • the pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 ⁇ m.
  • a photolithography method using a photosensitive resin composition is known as a typical manufacturing method of a color filter.
  • a photosensitive resin composition containing a carboxy group-containing resin capable of alkaline development is first applied onto a transparent substrate, dried, and then developed using image exposure and an alkaline developer.
  • a pattern is formed by curing by high-temperature treatment at 200 ° C. or higher.
  • the line width and film thickness change depending on the molecular weight and viscosity of the carboxy group-containing resin. If the stability of the carboxy group-containing resin over time is low, problems such as a decrease in the yield of the color filter have occurred.
  • Patent Documents 1 and 2 describe a method for producing a carboxy group-containing resin using specific conditions.
  • an object of the present invention is to provide a method for producing a carboxy group-containing resin-containing liquid having excellent stability over time and a method for stabilizing the carboxy group-containing resin.
  • the present inventors have found that the above-mentioned problems can be solved by producing a carboxy group-containing resin-containing liquid using a specific method. That is, the gist of the present invention lies below.
  • step A to obtain the first carboxy group-containing resin-containing liquid by reacting in an organic solvent.
  • a method for producing a carboxy group-containing resin-containing liquid which comprises the step B of adding water to the first carboxy group-containing resin-containing liquid to obtain a second carboxy group-containing resin-containing liquid.
  • a method for producing a carboxy group-containing resin-containing liquid [3] The method for producing a carboxy group-containing resin-containing liquid according to [1] or [2], wherein the polyhydric alcohol (e) is further added and reacted in the step A. [4] The method for producing a carboxy group-containing resin-containing liquid according to [3], wherein the polyhydric alcohol (e) contains trimethylolpropane. [5] The method for producing a carboxy group-containing resin-containing liquid according to any one of [1] to [4], wherein the polybasic acid dianhydride (c) contains a biphenyltetracarboxylic acid dianhydride.
  • [6] The method for producing a carboxy group-containing resin-containing liquid according to any one of [1] to [5], wherein the polybasic acid monoanhydride (d) contains a tetrahydrophthalic anhydride.
  • a method for producing an ink which comprises blending the carboxy group-containing resin-containing liquid produced by the production method according to any one of [1] to [6] as the alkali-soluble resin (A).
  • a method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator.
  • a method for producing a photosensitive resin composition which comprises blending the carboxy group-containing resin-containing liquid produced by the production method according to any one of [1] to [6] as the alkali-soluble resin (A).
  • the method for producing a photosensitive resin composition according to [8], wherein the photosensitive resin composition further contains (D) a coloring material.
  • a method for producing a cured product which comprises curing the photosensitive resin composition obtained by the production method according to [10] [8] or [9].
  • a method for producing a black matrix which comprises forming a black matrix using the cured product obtained by the production method according to [10].
  • a method for manufacturing an image display device which comprises using the cured product obtained by the manufacturing method according to [10] or the black matrix obtained by the manufacturing method according to [11].
  • a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, an organic solvent and water, and having a water content of 0.1% by mass or more and 1% by mass or less.
  • the carboxy group-containing resin-containing liquid according to [13] wherein the carboxy group-containing resin has a structure derived from the epoxy compound (a).
  • [18] Containing (A) an alkali-soluble resin, an organic solvent and (D) a coloring material, An ink in which the alkali-soluble resin (A) contains a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid according to any one of [13] to [17].
  • [20] A cured product obtained by curing the photosensitive resin composition according to [19].
  • [21] A black matrix formed by using the cured product according to [20].
  • An image display device comprising the cured product according to [20] or the black matrix according to [21].
  • [23] A reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d).
  • a method for stabilizing a carboxy group-containing resin which comprises adding water to a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, which is obtained by reacting the above in an organic solvent.
  • (meth) acrylic means “acrylic and / or methacrylic", and the same applies to "(meth) acrylate” and "(meth) acryloyl”.
  • the total solid content means all the components other than the organic solvent and water contained in the photosensitive resin composition or the ink described later.
  • the "photosensitive resin composition” may be referred to as “resist”.
  • the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
  • the "amine value” represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH, unless otherwise specified. .. The measurement method will be described later.
  • the method for producing a carboxy group-containing resin-containing liquid of the present invention comprises a reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), and a polybasic acid dianhydride (c). , The step A of reacting the polybasic acid monoanhydride (d) in an organic solvent to obtain a carboxy group-containing resin-containing liquid (also referred to as “first carboxy group-containing resin-containing liquid”), and the above-mentioned step A.
  • the carboxy group-containing resin-containing liquid may be a suspension, a dispersion liquid or a solution as long as it is a liquid mixture containing a carboxy group-containing resin, and is preferably a carboxy group-containing resin-containing solution.
  • the epoxy compound (a) is not particularly limited as long as it is a compound having an epoxy group.
  • bisphenol A type epoxy resin for example, "jER (registered trademark. The same shall apply hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.
  • alcoholic properties of bisphenol A type epoxy resin for example, "NER-1302” manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.)
  • bisphenol F type resin for example, "jER807” manufactured by Mitsubishi Chemical Corporation.
  • an epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the bisphenol F type epoxy resin with epichlorohydrin for example, "NER” manufactured by Nippon Kayaku Co., Ltd. -7406 "(epoxy equivalent 350, softening point 66 ° C)
  • bisphenol S type epoxy resin for example, biphenyl glycidyl ether (for example,” YX-4000 “manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, Nippon Kayaku).
  • Trisphenol methane type epoxy resin for example,“ EPPN (registered trademark; the same shall apply hereinafter) -501 ”,“ EPPN-502 ”,“ EPPN-503 ”) manufactured by Nippon Kayaku Co., Ltd., Alicyclic epoxy resin (“Selokiside (registered trademark; the same applies hereinafter) 2021P” manufactured by Daicel Co., Ltd., “Selokiside EHPE”), an epoxy resin obtained by glycidylizing a phenol resin produced by the reaction of dicyclopentadiene and phenol (for example, DIC Co., Ltd.) "EXA-7200” manufactured by Nippon Kayaku Co., Ltd., "NC-7300” manufactured by Nippon Kayaku Co., Ltd., a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the following general formula (a1) to The epoxy compound represented by (a6) can be preferably used
  • b11 indicates an average value and indicates a number from 0 to 10.
  • R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 11s existing in one molecule may be the same or different from each other.
  • R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 21s existing in one molecule may be the same or different from each other.
  • X represents a linking group represented by the following general formula (a3-1) or (a3-2).
  • the molecular structure contains one or more adamantane structures.
  • b13 indicates an integer of 2 or 3.
  • (a3-1) is preferable for X and 2 is preferable for b13 from the viewpoint of the patterning characteristics of the resist.
  • R 31 to R 34 and R 35 to R 37 each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent.
  • * in the formula represents a binding site in the formula (a3).
  • the formula (a3-1) preferably has two adamantyl groups and two hydrogen atoms from the viewpoint of the patterning characteristics of the resist.
  • the formula (a3-2) preferably has two adamantyl groups and one hydrogen atom from the viewpoint of the patterning characteristics of the resist.
  • p and q each independently represent an integer of 0 to 4
  • R 41 and R 42 each independently represent an alkyl group or a halogen atom having 1 to 20 carbon atoms.
  • R 43 and R 44 each independently represent an alkylene group having 1 to 5 carbon atoms.
  • x and y each independently represent an integer of 0 or more.
  • 0 is preferable for p, q, x, and y from the viewpoint of the patterning characteristics of the resist.
  • R 51 to R 54 are independently composed of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms
  • R 56 is an alkylene group having 1 to 5 carbon atoms independently.
  • k is an integer of 1 to 5
  • l is an integer of 0 to 13
  • m is an integer of 0 to 5 independently.
  • hydrogen atoms are preferable for R 51 to R 54
  • 2 is preferable for k
  • 0 is preferable for l and m.
  • R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 23s existing in one molecule may be the same or different from each other.
  • the epoxy compound represented by any of the general formulas (a1) to (a6) it is preferable to use the epoxy compound represented by (a3), (a4) or (a5).
  • the epoxy compound is more preferable, and the epoxy compound represented by (a5) is further preferable.
  • the unsaturated monobasic acid (b) may be any compound having only one acid group in one molecule and one or more radically polymerizable unsaturated bonds, and the acid group is preferably a carboxy group. ..
  • the acid group reacts with the epoxy group of the epoxy compound to form an intermediate in which a radically polymerizable double bond is introduced into the epoxy compound.
  • Examples of the unsaturated monobasic acid (b) include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, ⁇ -position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, and nitro.
  • Monocarboxylic acids such as cyano substituents, 2- (meth) acrylicyloxyethyl succinic acid, 2- (meth) acrylicyloxyethyl adipic acid, 2- (meth) acrylicyloxyethyl phthalic acid, 2- (meth) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) Acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acrylic ⁇ to leuroxybutyladipic acid, 2- (meth
  • an acid such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid
  • examples thereof include (meth) acrylic acid ester and (meth) acrylic acid dimer having one or more ethylene unsaturated groups and one carboxy group at the terminal by adding (anhydrous).
  • the unsaturated monobasic acid (b) is preferably an alkenylcarboxylic acid, and more preferably a (meth) acrylic acid.
  • Examples of the solvent used in the reaction for obtaining the intermediate include organic solvents, for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, ethylene glycol monomethyl ether acetate, and ethylene glycol mono.
  • organic solvents for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, ethylene glycol monomethyl ether acetate, and ethylene glycol mono.
  • Ethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene and xylene can be used.
  • propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferable, and prop
  • a known method can be used as a method for obtaining an intermediate by reacting the epoxy compound (a) with the unsaturated monobasic acid (b).
  • the epoxy compound (a) and the unsaturated monobasic acid (b) can be reacted at a temperature of 50 to 150 ° C. in a solvent in the presence of a catalyst and a polymerization inhibitor.
  • the catalyst examples include tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride.
  • a quaternary ammonium salt such as dodecyltrimethylammonium chloride can be used.
  • tertiary phosphine is preferable, and triphenylphosphine is more preferable, from the viewpoint of reaction yield.
  • polymerization inhibitor for example, hydroquinone, methylhydroquinone, trimethylhydroquinone, paramethoxyphenol, and 2,6-di-tert-butyl-4-cresol can be used.
  • paramethoxyphenol and 2,6-di-tert-butyl-4-cresol are preferable, and paramethoxyphenol is more preferable, from the viewpoint of reaction yield and resist sensitivity.
  • the epoxy compound (a), the unsaturated monobasic acid (b), the solvent used in the reaction for obtaining the intermediate, the catalyst, and the polymerization inhibitor may be used alone or in combination of two. The above may be used together.
  • the amount of the unsaturated monobasic acid (b) used is preferably in the range of 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the epoxy compound (a), and more preferably 0.8 to 1.2 equivalents. It is a range.
  • the amount of the unsaturated monobasic acid (b) By setting the amount of the unsaturated monobasic acid (b) to be equal to or higher than the lower limit, the amount of residual epoxy tends to decrease, and gelation during the reaction with the polybasic acid anhydride in step A tends to be suppressed. Further, by setting the amount to be used to the upper limit or less, there is a tendency that the unsaturated monobasic acid (b) can be suppressed from remaining as an unreacted product.
  • the polybasic acid dianhydride (c) may be a compound having only two acid anhydride groups in one molecule. From the viewpoint of the patterning characteristics of the resist, it is preferable to contain the compound represented by the general formula (c1).
  • A is a tetravalent organic group derived from polybasic acid dianhydride.
  • Examples of the polybasic acid dianhydride (c) represented by the general formula (c1) include biphenyltetracarboxylic acid dianhydride (BPDA), bicyclohexyltetracarboxylic acid dianhydride, pyromellitic acid anhydride, and benzophenone. Tetracarboxylic acid dianhydride can be used. Among these, biphenyltetracarboxylic acid dianhydride (BPDA) and pyromellitic acid anhydride are preferable, and biphenyltetracarboxylic acid dianhydride (BPDA) is more preferable from the viewpoint of the patterning property of the resist.
  • BPDA biphenyltetracarboxylic acid dianhydride
  • BPDA biphenyltetracarboxylic acid dianhydride
  • BPDA biphenyltetracarboxylic acid dianhydride
  • BPDA biphenyltetracarboxylic acid dianhydr
  • the polybasic acid anhydride (d) may be a compound having only one acid anhydride group in one molecule.
  • Anhydride and trimellitic acid anhydride can be used.
  • succinic acid anhydride, phthalic acid anhydride, and tetrahydrophthalic acid anhydride are preferable, and tetrahydrophthalic acid anhydride is more preferable, from the viewpoint of the patterning property of the resist.
  • polybasic acid dianhydride (c) and the polybasic acid monoanhydride (d) one type may be used alone, or two or more types may be used in combination.
  • An intermediate obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d) are used as an organic solvent.
  • a known method can also be used for the reaction in which the reaction is carried out to obtain the first carboxy group-containing resin-containing liquid.
  • the polybasic acid dianhydride (c) and the polybasic acid monoanhydride (d) can be additionally added to the intermediate solution containing the intermediate and reacted at a temperature of 50 to 150 ° C.
  • a polyhydric alcohol (e) may be further added and reacted.
  • polyhydric alcohol (e) for example, trimethylolpropane, pentaerythritol, and dipentaerythritol can be used.
  • trimethylolpropane is preferable from the viewpoint of resist sensitivity and stability over time.
  • the amount of the polyhydric alcohol (e) used is preferably 0.01 equivalent or more, more preferably 0.02 equivalent or more, relative to 1 equivalent of the unsaturated monobasic acid (b). Further, 1 equivalent or less is preferable, 0.7 equivalent or less is more preferable, 0.5 equivalent or less is further preferable, and 0.3 equivalent or less is particularly preferable. When it is at least the lower limit value, the stability with time tends to be improved, and when it is at least the upper limit value, the resist sensitivity tends to be improved. The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1 equivalent is preferable, 0.01 to 0.7 equivalent is more preferable, 0.02 to 0.5 equivalent is further preferable, and 0.02 to 0.3 equivalent is particularly preferable.
  • the amount of the polybasic acid dianhydride (c) to be used is preferably 0.1 equivalent or more, more preferably 0.3 equivalent or more, and 0.5 equivalent or more with respect to 1 equivalent of the polybasic acid monoanhydride (d). Is even more preferable. Further, 50 equivalents or less is preferable, 40 equivalents or less is more preferable, and 30 equivalents or less is further preferable. When the value is not less than the lower limit, the adhesion of the resist tends to be improved, and when the value is not more than the upper limit, the residue of the resist tends to be reduced. The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 50 equivalents are preferred, 0.3 to 40 equivalents are more preferred, and 0.5 to 30 equivalents are even more preferred.
  • step B water is added to the first carboxy group-containing resin-containing liquid obtained in step A to obtain a second carboxy group-containing resin-containing liquid.
  • step B it is possible to suppress changes in the molecular weight and viscosity of the carboxy group-containing resin in the obtained carboxy group-containing resin-containing liquid during storage, and to stabilize the carboxy group-containing resin.
  • Water may be added alone or as a mixture of water and the organic solvent mentioned as the solvent used in the reaction for obtaining an intermediate.
  • the temperature of the carboxy group-containing resin-containing liquid at the time of addition is preferably 20 ° C to 80 ° C, more preferably 30 ° C to 70 ° C, further preferably 40 ° C to 60 ° C, and particularly preferably 45 ° C to 55 ° C.
  • water can be uniformly dispersed and dissolved in the carboxy group-containing resin-containing liquid. It is preferable to add water while stirring the carboxy group-containing resin-containing liquid. As a result, water can be uniformly dispersed and dissolved in the carboxy group-containing resin-containing liquid.
  • the water content of the second carboxy group-containing resin-containing liquid is preferably 0.1% by mass or more, more preferably 0.12% by mass or more, still more preferably 0.14% by mass or more. , 0.16% by mass or more is particularly preferable, and 0.18% by mass or more is particularly preferable. Further, 1% by mass or less is preferable, 0.8% by mass or less is more preferable, 0.6% by mass or less is further preferable, 0.5% by mass or less is particularly preferable, and 0.4% by mass or less is particularly preferable.
  • the value By setting the value to the lower limit or higher, the stability over time tends to be improved. Further, when the value is not more than the upper limit, the adhesion of the resist tends to be improved.
  • the above upper and lower limits can be combined arbitrarily.
  • 0.1 to 1% by mass is preferable, 0.12 to 0.8% by mass is more preferable, 0.14 to 0.6% by mass is further preferable, and 0.16 to 0.5% by mass is particularly preferable.
  • 0.18 to 0.4% by mass is particularly preferable.
  • the water content of the carboxy group-containing resin-containing liquid can be calculated by the Karl Fischer titer measurement method described in JIS K0113 (2005).
  • Various moisture meters can be used, and examples thereof include MKA-610 manufactured by Kyoto Denshi Kogyo Co., Ltd.
  • the acid value of the carboxy group-containing resin produced by the method of the present invention is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. Further, 250 mgKOH / g or less is preferable, 200 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable.
  • the value By setting the value to the lower limit or more, the residue of the resist tends to be reduced. Further, when the value is not more than the upper limit, the adhesion of the resist tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 250 mgKOH / g is preferable, 30 to 200 mgKOH / g is more preferable, 50 to 150 mgKOH / g is further preferable, and 80 to 130 mgKOH / g is particularly preferable.
  • the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid produced by the production method of the present invention is also referred to as "carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid produced by the production method of the present invention”.
  • the weight average molecular weight is preferably 3000 or more, more preferably 5000 or more, further preferably 8000 or more, and particularly preferably 12000 or more. Further, 22000 or less is preferable, and 21000 or less is more preferable. By setting the value to the lower limit or more, the adhesion of the resist tends to be improved. Further, when the value is not more than the upper limit, the residue of the resist tends to be reduced.
  • the above upper and lower limits can be combined arbitrarily. For example, 3000 to 22000 is preferable, 5000 to 22000 is more preferable, 8000 to 21000 is further preferable, and 12000 to 21000 is particularly preferable.
  • the carboxy group-containing resin-containing liquid of the present invention contains a carboxy group-containing resin, an organic solvent and water, and has a water content of 0.1% by mass or more and 1% by mass or less.
  • water content is within the above range, changes in the molecular weight and viscosity of the carboxy group-containing resin in the carboxy group-containing resin-containing liquid during storage can be suppressed, and the carboxy group-containing resin can be stabilized. .. Further, the adhesion of the resist using the carboxy group-containing resin-containing liquid tends to be improved.
  • the water content of the carboxy group-containing resin-containing liquid is 0.1% by mass or more and 1% by mass or less, more preferably 0.12% by mass or more, further preferably 0.14% by mass or more, and 0.16% by mass.
  • the above is particularly preferable, and 0.18% by mass or more is particularly preferable. Further, 0.8% by mass or less is more preferable, 0.6% by mass or less is further preferable, 0.5% by mass or less is particularly preferable, and 0.4% by mass or less is particularly preferable.
  • the above upper limit and lower limit can be arbitrarily combined, and for example, 0.12% by mass or more and 0.8% by mass or less are preferable, 0.14% by mass or more and 0.6% by mass or less is more preferable, and 0.16% by mass is preferable.
  • % Or more and 0.5% by mass or less are more preferable, and 0.18% by mass or more and 0.4% by mass or less are particularly preferable.
  • the value By setting the value to the lower limit or higher, the stability over time tends to be improved. Further, when the value is not more than the upper limit value, the adhesion of the resist tends to be improved.
  • the carboxy group-containing resin-containing liquid of the present invention is preferably a carboxy group-containing resin-containing liquid produced by the production method of the present invention.
  • the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the epoxy compound (a).
  • the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the unsaturated monobasic acid (b).
  • the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the polybasic acid dianhydride (c).
  • the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the polybasic acid monoanhydride (d).
  • the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the polyhydric alcohol (e).
  • Preferred types and amounts of the epoxy compound (a), unsaturated monobasic acid (b), polybasic acid dianhydride (c), polybasic acid monoanhydride (d), polyhydric alcohol (e), etc. The method for producing a carboxy group-containing resin-containing liquid is the same as the above-mentioned type and blending amount.
  • the organic solvent contained in the carboxy group-containing resin-containing liquid of the present invention can be preferably used.
  • the method for producing a photosensitive resin composition of the present invention is a method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator.
  • the alkali-soluble resin includes a carboxy group-containing resin-containing liquid produced by the production method of the present invention.
  • the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and is a carboxy of the present invention as (A) an alkali-soluble resin.
  • photosensitive resin composition in the present invention Contains a carboxy group-containing resin derived from a group-containing resin-containing liquid.
  • the photosensitive resin composition in the present invention contains, as (A) an alkali-soluble resin, a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid of the present invention, that is, a carboxy group-containing resin produced by the production method of the present invention.
  • a carboxy group-containing resin derived from the liquid By containing the carboxy group-containing resin derived from the liquid, it is possible to suppress changes in the molecular weight and viscosity of the carboxy group-containing resin in the carboxy group-containing resin-containing liquid during storage and stabilize the carboxy group-containing resin.
  • the alkali-soluble resin may contain other alkali-soluble resins.
  • alkali-soluble resins include those in which the solubility of the exposed portion and the non-exposed portion in alkaline development changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed.
  • it is preferably an alkali-soluble resin having a carboxy group.
  • those having an ethylenically unsaturated group are preferable, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxy group is more preferable.
  • Specific examples thereof include epoxy (meth) acrylate resins and acrylic copolymer resins having a carboxy group, and specific examples thereof include (A1-1), (A2-1), (A2-2), and (A1-2), which will be described later.
  • Examples thereof include the alkali-soluble resins described as A2-3) and (A2-4). These may be used alone or in combination of two or more. Among the above, an epoxy (meth) acrylate resin (A1-1) having a carboxy group is particularly preferable.
  • a polymer resin having an acidic functional group such as a hydroxyl group, a carboxy group, a phosphoric acid group, or a sulfonic acid group is applied as the polymer resin in order to dissolve the non-exposed portion in the alkaline developing solution.
  • a polymer resin having a carboxy group is preferable from the viewpoint of solubility in an alkaline developer.
  • the phosphate group and the sulfonic acid group have higher acidity than the carboxy group, they easily react with the initiator, the monomer, the dispersant, and other additives having a basic group in the photosensitive resin composition. , Storage stability may deteriorate.
  • Examples of the epoxy (meth) acrylate resin having a carboxy group include the following epoxy (meth) acrylate resin (A1-1).
  • ⁇ Epoxy (meth) acrylate resin (A1-1)> An alkali-soluble resin obtained by adding an unsaturated monobasic acid to an epoxy compound and further reacting it with a polybasic acid monoanhydride.
  • Epoxy (meth) acrylate resin (A1-1) having a carboxy group and an ethylenically unsaturated group bond examples include bisphenol A type epoxy resin (for example, "jER (registered trademark; the same applies hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, bisphenol. Epoxy obtained by the reaction of the alcoholic hydroxyl group of the A-type epoxy resin with epichlorohydrin (for example, "NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, Mitsubishi).
  • bisphenol A type epoxy resin for example, "jER (registered trademark; the same applies hereinafter) 828", “jER1001", “jER1002", “jER1004", etc.
  • NER-7406 manufactured by Kayakusha (epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, “YX-4000” manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy Resins (for example, "EPPN-201” manufactured by Nippon Kayaku Co., Ltd., "EP-152", “EP-154" manufactured by Mitsubishi Chemical Corporation, “DEN-438” manufactured by Dow Chemical Corporation), (o, m, p-) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark.
  • b11 indicates an average value and indicates a number from 0 to 10.
  • R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 11s existing in one molecule may be the same or different from each other.
  • R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 21s existing in one molecule may be the same or different from each other.
  • X represents a linking group represented by the following general formula (a3-1) or (a3-2).
  • the molecular structure contains one or more adamantane structures.
  • b13 indicates an integer of 2 or 3.
  • R 31 to R 34 and R 35 to R 37 each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent.
  • * in the formula represents a binding site in the formula (a3).
  • the formula (a3-1) preferably has two adamantyl groups and two hydrogen atoms, respectively, from the viewpoint of the patterning characteristics of the resist.
  • the formula (a3-2) preferably has two adamantyl groups and one hydrogen atom from the viewpoint of the patterning characteristics of the resist.
  • p and q each independently represent an integer of 0 to 4
  • R 41 and R 42 each independently represent an alkyl group or a halogen atom having 1 to 20 carbon atoms.
  • R 43 and R 44 each independently represent an alkylene group having 1 to 5 carbon atoms.
  • x and y each independently represent an integer of 0 or more.
  • R 51 to R 54 are independently composed of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and
  • R 56 is an alkylene group having 1 to 5 carbon atoms independently.
  • k is an integer of 1 to 5
  • l is an integer of 0 to 13
  • m is an integer of 0 to 5 independently.
  • R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group.
  • the plurality of R 23s existing in one molecule may be the same or different from each other.
  • an epoxy compound represented by any of the general formulas (a1), (a2) or (a6) it is preferable to use an epoxy compound represented by any of the general formulas (a1), (a2) or (a6).
  • Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, ⁇ -position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products.
  • Monocarboxylic acids such as 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxy Ethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxy Propyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl Adipic acid, 2- (meth)
  • a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the terminal such as pentaerythritol tri (meth) acrylate, and (maleic) succinic acid
  • Acrylic acid dimer can be mentioned.
  • (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
  • a method for adding an unsaturated monobasic acid a known method can be used.
  • the unsaturated monobasic acid can be reacted with the epoxy compound at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst.
  • the catalyst used here includes tertiary phosphine such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amine such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride.
  • Quaternary ammonium salts such as dodecyltrimethylammonium chloride can be used.
  • the epoxy compound, unsaturated monobasic acid, and catalyst may be used alone or in combination of two or more.
  • the amount of the unsaturated monobasic acid used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound.
  • polybasic acid monoanhydride examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and chlorendic acid. , One or more selected from monoanhydrides of methyltetrahydrophthalic acid.
  • maleic acid succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid anhydrides.
  • phthalic acid tetrahydrophthalic acid, a monoanhydride.
  • a known method can also be used for the addition reaction of polybasic acid monoanhydride, and the desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of unsaturated monobasic acid to the epoxy compound. ..
  • the amount of the polybasic acid monoanhydride component added is preferably such that the acid value of the produced carboxy group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and more preferably 20 to 140 mgKOH / g. It is preferably in the range of g. When the value is equal to or higher than the lower limit, the alkali developability tends to be good. Further, when the value is not more than the upper limit, the curability tends to be good.
  • the acid value of the epoxy (meth) acrylate resin (A1-1) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, and 200 mgKOH / g or less. It is preferably present, and more preferably 150 mgKOH / g or less.
  • the value is equal to or higher than the lower limit, the developability tends to be good. Further, the alkali resistance tends to be improved by setting the value to the upper limit or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH / g is preferable, 50 to 200 mgKOH / g is more preferable, and 80 to 150 mgKOH / g is further preferable.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (A1-1) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more. 2500 or more is particularly preferable. Further, 20000 or less is preferable, 15000 or less is more preferable, 10000 or less is further preferable, 8000 or less is further preferable, and 7000 or less is particularly preferable. When the value is equal to or higher than the lower limit, the sensitivity, coating film strength, and alkali resistance tend to be good.
  • the value to the upper limit or less, there is a tendency that the developability and the resolubility can be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 1000 to 20000 is preferable, 1000 to 15000 is more preferable, 1500 to 10000 is further preferable, 2000 to 8000 is further preferable, and 2500 to 7000 is particularly preferable.
  • the acrylic copolymer resin include Japanese Patent Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japan.
  • the following resins (A2-1) to (A2-4) are preferably used, and among them, the (A2-1) resin is particularly preferable.
  • the photosensitive resin composition in the present invention contains at least one of (A1-1), (A2-1), and (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group from the viewpoint of sensitivity. Is even more preferable. From the viewpoint of surface curability, the photosensitive resin composition in the present invention particularly preferably contains an epoxy (meth) acrylate resin (A1-1) as an alkali-soluble resin containing an ethylenically unsaturated group.
  • the content ratio of the alkali-soluble resin (A) is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more with respect to the total solid content of the photosensitive resin composition. It is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
  • the value to the lower limit or more By setting the value to the lower limit or more, the solubility of the unexposed portion in the developing solution tends to be good. Further, by setting the value to the upper limit or less, excessive penetration of the developing solution into the exposed portion can be suppressed, and the sharpness and adhesion of the image tend to be improved.
  • the photosensitive resin composition in the present invention contains another alkali-soluble resin as the (A) alkali-soluble resin, the above-mentioned (A1-1), (A2-1), ( It is preferable to contain at least one of A2-2), (A2-3) and (A2-4).
  • the content ratio thereof is preferably 30% by mass or less, preferably 20% by mass, based on the total amount of (A) alkali-soluble resin from the viewpoint of resist patterning. % Or less is more preferable, and 10% by mass or less is further preferable, and it may not be contained.
  • the photosensitive resin composition in the present invention contains (B) a photopolymerizable monomer from the viewpoint of sensitivity and the like.
  • the (B) photopolymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, may be referred to as “ethylenic monomer”). Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, and carboxylic acids having one ethylenically unsaturated bond, and esters of polyvalent or monovalent alcohols. ..
  • the photopolymerizable monomer (B) it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and usually.
  • the number is 10 or less, preferably 8 or less.
  • polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a polyhydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid examples include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • Pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate
  • acrylic acid ester of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylic acid in which the acrylate of these exemplary compounds is replaced with methacrylate.
  • ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include acrylic acid esters and methacrylics of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogalloltriacrylate. Acid esters can be mentioned.
  • the ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but typical specific examples include acrylic acid, phthalic acid, and Examples thereof include a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol and glycerin.
  • a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted.
  • Urethane (meth) acrylates such as those obtained by the above; epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; phthal Allyl esters such as diallylic acid; vinyl group-containing compounds such as divinylphthalate are useful. These may be used alone or in combination of two or more.
  • the content ratio of the photopolymerizable monomer (B) is not particularly limited, but is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, based on the total solid content of the photosensitive resin composition. It is more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the content of the photopolymerizable monomer (b) is usually 1% by mass or more, preferably 5% by mass or more.
  • the photocuring due to ultraviolet irradiation is improved and the alkali developability tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 90% by mass is preferable, 1 to 70% by mass is more preferable, 1 to 50% by mass is further preferable, 5 to 30% by mass is further preferable, and 5 to 20% by mass is particularly preferable. Mass% is particularly preferred.
  • the photosensitive resin composition in the present invention contains (C) a photopolymerization initiator.
  • the photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a sensitizing dye may be added and used.
  • the photopolymerization initiator for example, a metallocene compound containing a titanosen compound described in JP-A-59-152396 and JP-A-61-151197 of Japan; Japanese Patent Application Laid-Open No. 2000-56118. Hexaaryl-biimidazole derivative according to Japanese Patent Application Laid-Open No. 10-39503, halomethylated oxadiazole derivative, halomethyl-s-triazine derivative, N-aryl- ⁇ -amino acids such as N-phenylglycine, N.
  • -Radical activators such as aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, etc. Examples thereof include the oxime ester derivative described in 1.
  • titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoropheni-1-yl).
  • Dicyclopentadienyl Titanium Bis (2,3,5,6-Tetrafluoropheni-1-yl), Dicyclopentadienyl Titanium Bis (2,4,6-Trifluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopentadienyl) Titanium Bis (2,3,4,5,6-pentafluoropheni-1-yl), di (methylcyclopentadienyl) titanium bis (2,6-difluoropheni-1-yl), dicyclopentadienyl titanium [ 2,6-Di-fluoro-3- (pyro-1-yl) -pheni-1-yl].
  • biimidazole derivatives examples include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole.
  • Dimeric, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxy) Phenyl) -4,5-diphenylimidazole dimer can be mentioned.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[ ⁇ - (2'-).
  • Benzofuryl) vinyl] -1,3,4-oxadiazole 2-trichloromethyl-5-[ ⁇ - (2'-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole
  • 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole can be mentioned.
  • halomethyl-s-triazine derivatives examples include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-Triazine can be mentioned.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-).
  • oxime derivatives are particularly useful in terms of sensitivity.
  • oxime ester compounds are preferable from the viewpoint of adhesion to the substrate.
  • an alkali-soluble resin containing a phenolic hydroxyl group is used, it may be disadvantageous in terms of sensitivity.
  • the photopolymerization initiator of an oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, so that it is highly sensitive in a small amount and has a thermal reaction. It is possible to design a photosensitive resin composition that is stable and highly sensitive in a small amount.
  • an oxime ester-based compound containing a optionally substituted carbazolyl group (a group having a optionally substituted carbazole ring) from the viewpoint of light absorption of an exposure light source for i-ray (365 nm). This structural property is well expressed and is more preferable.
  • the market demands a black matrix with a high degree of shading and a thin film, and the pigment concentration is also increasing. It is especially effective in such situations.
  • oxime ester compound examples include a compound containing a structural portion represented by the following general formula (22), and preferably an oxime ester compound represented by the following general formula (23).
  • R 22 may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number of carbon atoms.
  • An aminoalkylcarbonyl group, an allylloyl group having 7 to 20 carbon atoms, a heteroallyloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.
  • R 21a is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, which may be substituted with hydrogen, respectively.
  • An alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown.
  • R 21b represents any substituent, including aromatic or heteroaromatic rings.
  • R 22a represents the same group as R 22 in the above formula (22).
  • the R 22 in the general formula (22) and the R 22a in the general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group of.
  • the R 21a in the above general formula (23) is preferably substituted with an unsubstituted linear alkyl group such as a methyl group, an ethyl group or a propyl group, a cycloalkylalkyl group, or an N-acetyl-N-acetoxyamino group.
  • an unsubstituted linear alkyl group such as a methyl group, an ethyl group or a propyl group, a cycloalkylalkyl group, or an N-acetyl-N-acetoxyamino group.
  • Propyl group can be mentioned.
  • examples of R 21b in the above general formula (23) include a carbazolyl group which may be substituted, a thioxanthonyl group which may be substituted, and a phenylsulfide group which may be substituted.
  • R 21b in the above general formula (23) is a carbazolyl group which may be substituted is more preferable for the above-mentioned reason.
  • an aryl group having 6 to 25 carbon atoms which may be substituted an arylcarbonyl group having 7 to 25 carbon atoms which may be substituted, a heteroaryl group having 5 to 25 carbon atoms which may be substituted, and a substituted moiety.
  • a carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms and a nitro group may be preferable.
  • a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoil group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. Further, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.
  • photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but the present invention is not limited to these compounds.
  • ketooxime ester compound examples include a compound containing a structural portion represented by the following general formula (24), and preferably a ketooxime ester compound represented by the following general formula (25).
  • R 24 is synonymous with R 22 in the general formula (22).
  • R 23a may be substituted with a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a heteroarylalkyl group having 1 to 20 carbon atoms, respectively.
  • alkoxycarbonylalkyl group with 3 to 20 carbon atoms alkoxycarbonylalkyl group with 3 to 20 carbon atoms, phenoxycarbonylalkyl group with 8 to 20 carbon atoms, alkylthioalkyl group with 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group with 1 to 20 carbon atoms or heteroarylthio Alkyl group, aminoalkyl group with 1 to 20 carbon atoms, alkanoyl group with 2 to 12 carbon atoms, alkenoyl group with 3 to 25 carbon atoms, cycloalkanoyl group with 3 to 8 carbon atoms, allylloyl group with 7 to 20 carbon atoms, A heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atom
  • R 23b represents any substituent, including aromatic or heteroaromatic rings.
  • - Polyethynylene group (-(C ⁇ C) r- ) or a group composed of a combination thereof can be mentioned (where r is an integer of 0 to 3).
  • R 24a may be substituted with an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, and carbon.
  • the R 24 in the general formula (24) and the R 24a in the general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group and allyloyl group having 7 to 20 carbon atoms can be mentioned.
  • the R 23a in the above general formula (25) preferably includes an unsubstituted ethyl group, a propyl group, a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
  • examples of R 23b in the above general formula (25) include a optionally substituted carbazoyl group and an optionally substituted phenylsulfide group.
  • Specific examples of the ketooxime ester-based compound suitable for the present invention include, but are not limited to, the compounds exemplified below.
  • oxime and ketooxyester compounds are known compounds themselves, and are, for example, a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 and Japanese Patent Application Laid-Open No. 2006-36750. It is a kind.
  • the above photopolymerization initiator may be used alone or in combination of two or more.
  • benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like.
  • Anthraquinone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2 -Phenylacetphenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1, -Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanol, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, etc.
  • the photopolymerization initiator may be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity.
  • sensitizing dyes include the xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-239703.
  • Japanese Patent Application Laid-Open No. 6-19240 Japanese Patent Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Publication No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Japanese Patent Application Laid-Open No. 58-15503, Japanese Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No.
  • amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable.
  • amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable.
  • Benzophenone compounds such as benzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (P-Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- ( p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (P-Dimethylaminophenyl) pyr
  • the content of the photopolymerization initiator (C) is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, based on the total solid content of the photosensitive resin composition. It is more preferably 4% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. Sensitivity tends to improve when the value is equal to or higher than the lower limit. Further, when the value is not more than the upper limit, the solubility of the unexposed portion in the developing solution tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 30% by mass is preferable, 1 to 20% by mass is more preferable, 2 to 15% by mass is further preferable, 3 to 10% by mass is further preferable, and 4 to 8% by mass is particularly preferable.
  • the blending ratio of the sensitizing dye in the photosensitive resin composition is usually 0 to 20% by mass, preferably 0 to 15% by mass, and further, in the total solid content in the photosensitive resin composition. It is preferably 0 to 10% by mass.
  • the coloring material refers to a material that colors the photosensitive resin composition in the present invention.
  • dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.
  • pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment and black pigment can be used.
  • various inorganic pigments can be used in addition to azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolenone-based, dioxazine-based, indanthrone-based, and perylene-based organic pigments. Is.
  • pigments that can be used in the present invention are shown below by pigment numbers.
  • the terms such as "CI Pigment Red 2" listed below mean the color index (CI).
  • examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172
  • C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 can be mentioned.
  • Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned.
  • C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60 more preferably C.I. I. Pigment Blue 15: 6, 60 can be mentioned.
  • Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be mentioned. Among these, preferably C.I. I. Pigment Greens 7, 36 and 58 can be mentioned.
  • yellow pigment examples include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189,
  • C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
  • orange pigment examples include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned.
  • C.I. I. Pigment Orange 38, 64, 71 can be mentioned.
  • C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned.
  • C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23, 29 can be mentioned.
  • a black coloring material can be used as the (D) coloring material.
  • the black color material may be a black color material alone or may be a mixture of red, green, blue color materials and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes. Examples of the color materials that can be mixed and used to prepare the black color material include Victoria Pure Blue (42595), Auramine O (41000), Cachilon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), and Rhodamine B ( 45170), Safranin OK70: 100 (50240), Eriograusin X (42080), No.
  • black color material examples include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
  • carbon black is preferable from the viewpoint of light shielding rate and image characteristics. Examples of carbon black include the following carbon blacks.
  • titanium black As an example of other black pigments, titanium black, aniline black, iron oxide-based black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.
  • the pigment for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide can be used.
  • a plurality of these various pigments can be used in combination.
  • a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination for adjusting the chromaticity.
  • the average particle size of the pigment may be any as long as it can develop a desired color when it is used as a colored layer of a color filter, and is not particularly limited and varies depending on the type of pigment used, but is within the range of 10 to 100 nm. It is preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 70 nm.
  • the average particle size of the pigment is in the above range, the color characteristics of the liquid crystal display device manufactured by using the photosensitive resin composition of the present invention tend to be high quality.
  • the average particle size of carbon black is preferably 60 nm or less, more preferably 50 nm or less, more preferably 20 nm or more, for example, preferably 20 to 50 nm, and even more preferably 20 to 60 nm.
  • the average particle size of the pigment containing carbon black can be obtained by a method of directly measuring the size of the primary particles from an electron micrograph.
  • the minor axis diameter and the major axis diameter of each primary particle are measured, and the average thereof is taken as the particle size of the particle.
  • the volume (mass) of each particle is obtained by approximating it to a rectangular parallelepiped having the obtained particle size, and the volume average particle size is obtained and used as the average particle size.
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • the photosensitive resin composition in the present invention contains (D) a coloring material
  • a coloring material it is preferable that the photosensitive resin composition contains at least a pigment as the coloring material, but in addition, a dye is used in combination as long as it does not affect the effect of the present invention. May be good.
  • dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
  • azo dye examples include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7 can be mentioned.
  • anthraquinone dye examples include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 can be mentioned.
  • a phthalocyanine dye for example, C.I. I. Pad Blue 5 and the like can be used as quinoneimine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are used as quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I.
  • C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 can be mentioned.
  • the content ratio of the (D) coloring material is usually in the range of 1 to 70% by mass with respect to the total solid content in the photosensitive resin composition. You can choose with. Within this range, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 40% by mass or more is particularly preferable, and 60% by mass or less is more preferable.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 70% by mass is preferable, 20 to 70% by mass is more preferable, 30 to 60% by mass is further preferable, and 40 to 60% by mass is particularly preferable.
  • the photosensitive resin composition in the present invention can be used for various purposes as described later, but excellent image forming property is particularly effective when used for forming a black matrix for a color filter. ..
  • (D) use a black color material such as carbon black or titanium black described above, or mix multiple types of color materials other than black and adjust to black. Just do it.
  • the photosensitive resin composition in the present invention is used for forming a black matrix, it is necessary to increase the concentration of the black colorant in order to increase the degree of light shielding.
  • the content ratio of the black color material is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more with respect to the total solid content of the photosensitive resin composition.
  • 70% by mass or less is preferable, and 65% by mass or less is more preferable.
  • the above upper limit and lower limit can be arbitrarily combined. For example, 40 to 70% by mass is preferable, 45 to 70% by mass is more preferable, and 50 to 65% by mass is further preferable.
  • the content ratio of the (D) coloring material is usually 20 parts by mass or more, preferably 30 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. More than parts, more preferably 40 parts by mass or more, still more preferably 60 parts by mass or more, still more preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and usually 500 parts by mass. Parts or less, preferably 300 parts by mass or less, more preferably 280 parts by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 20 to 500 parts by mass is preferable, 30 to 500 parts by mass is more preferable, 40 to 500 parts by mass is further preferable, 60 to 300 parts by mass is more preferable, 80 to 300 parts by mass is particularly preferable, and 120 to 280 parts is particularly preferable. The parts by mass are particularly preferable, and 160 to 280 parts by mass are most preferable.
  • the photosensitive composition in the present invention contains (D) a coloring material
  • a coloring material it is important to finely disperse the coloring material and stabilize the dispersed state thereof in order to ensure quality stability.
  • a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxy group; a phosphate group; a sulfonic acid group; or these groups; a primary, secondary or tertiary amino group.
  • a quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable.
  • a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferable.
  • a polymer dispersant having these basic functional groups the dispersibility tends to be good.
  • polymer dispersant examples include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ether-based dispersions.
  • examples thereof include agents, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • EFKA registered trademark, manufactured by EFKA
  • Disperbyk registered trademark, manufactured by Big Chemie
  • Disparon registered trademark, manufactured by Kusumoto Kasei
  • SOLSPERSE registered trademark, manufactured by Lubrizol
  • KP made by Shinetsu Chemical Industry Co., Ltd.
  • Polyflow or Floren registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.
  • Azisper registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.
  • These polymer dispersants may be used alone or in combination of two or more.
  • the dispersant preferably contains a urethane-based polymer dispersant having a basic functional group and / or an acrylic polymer dispersant, and the urethane-based polymer dispersant is used. It is more preferable to include it in terms of adhesion. Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and / or a polyether bond is preferable.
  • the weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less.
  • Mw weight average molecular weight
  • the above upper and lower limits can be combined arbitrarily. For example, 700 to 100,000 is preferable, 700 to 50,000 is more preferable, and 1,000 to 30,000 is even more preferable.
  • the urethane-based and acrylic polymer dispersants include Disperbyk 160 to 167, 182 series (all urethane-based) and Disperbyk2000, 2001 (all acrylic-based) (all manufactured by Big Chemie).
  • Disperbyk 167 and 182 are particularly preferable urethane-based polymer dispersants having the above-mentioned basic functional groups and having polyester and / or polyether bonds and having a weight average molecular weight of 30,000 or less.
  • a preferable chemical structure as a urethane-based polymer dispersant include a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000 in the same molecule.
  • examples thereof include a dispersed resin having a weight average molecular weight of 1000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group.
  • polyisocyanate compounds examples include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, trizine diisocyanate and the like.
  • the polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
  • an isocyanate trimer As a method for producing an isocyanate trimer, the polyisocyanate is subjected to an isocyanate group using an appropriate trimerization catalyst, for example, a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like.
  • trimerization catalyst for example, a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like.
  • trimerization catalyst for example, a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like.
  • polyether glycol As a compound having one or two hydroxyl groups in the same molecule and having an average molecular weight of 300 to 10,000, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one-terminal hydroxyl group of these compounds have 1 to 1 carbon atoms. Examples thereof include those analkylated with 25 alkyl groups and mixtures of two or more of these.
  • polyether glycol examples include a polyether diol, a polyether ester diol, and a mixture of two or more of these.
  • polyether diol examples include those obtained by using alkylene oxide alone or in copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and them. A mixture of two or more of the above can be mentioned.
  • Polyester ester diols are obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly). Oxytetramethylene) adipate can be mentioned.
  • the most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
  • polyester glycols examples include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene).
  • Glycol dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol , 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl Alicyclic glycols such as -2,5-hexanediol, 1,8-octamethylene glyco
  • Xylylene glycol aromatic glycols such as bishydroxyethoxybenzene, N-alkyldialkanolamines such as N-methyldiethanolamine, etc.
  • aromatic glycols such as bishydroxyethoxybenzene, N-alkyldialkanolamines such as N-methyldiethanolamine, etc.
  • Polylactone diols or polylactone monools obtained by using methylene adipate, polyethylene / propylene adipate, etc., or the above diols or monovalent alcohols having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone and Examples thereof include a mixture of two or more of these.
  • the most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.
  • polycarbonate glycol examples include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate
  • polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Can be mentioned. These may be used alone or in combination of two or more.
  • the number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.
  • active hydrogen that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom
  • active hydrogen include a hydrogen atom in a functional group such as a hydroxyl group, an amino group and a thiol group, and among them, an amino group, particularly a first-class one.
  • the hydrogen atom of the amino group of is preferable.
  • the tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.
  • an amino group having an active hydrogen and a tertiary amino group in the same molecule N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-di
  • Examples of the nitrogen-containing heterocycle when the tertiary amino group has a nitrogen-containing heterocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indol ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzotriazole.
  • N-containing hetero 5-membered ring such as ring, benzoxazole ring, benzothiazole ring, benzothiazol ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, aclysine ring, isoquinoline ring and other nitrogen-containing hetero 6-membered rings.
  • ring benzoxazole ring
  • benzothiazole ring benzothiazol ring
  • pyridine ring pyridazine ring
  • pyrimidine ring pyrimidine ring
  • triazine ring quinoline ring
  • aclysine ring isoquinoline ring and other nitrogen-containing hetero 6-membered rings.
  • an imidazole ring or a triazole ring is preferable.
  • these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole.
  • Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1.
  • 2,4-Triazole 4-amino-4H-1,2,4-Triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-Diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole.
  • N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.
  • the preferable blending ratio of the raw material for producing a urethane-based polymer dispersant is 10 to 200 for a compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 with respect to 100 parts by mass of the polyisocyanate compound.
  • mass preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule. It is a mass part.
  • the urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin.
  • the solvent used in the production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene and xylene.
  • Hydrocarbons such as hexane, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N- Aprotonic polar solvents such as methylpyrrolidone and dimethylsulfoxide are used. These may be used alone or in combination of two or more.
  • a urethanization reaction catalyst is usually used.
  • this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stanas octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine.
  • tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stanas octoate
  • iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine.
  • primary amine type One type or two or more types of primary amine type can be mentioned.
  • the tertiary amine value of the dispersant is expressed by the amount of base per 1 g of solid content excluding the solvent in the dispersant sample and the equivalent amount of KOH, and can be measured by the following method. Weigh 0.5-1.5 g of the dispersant sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L HClO 4 (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. The amine value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
  • Amine value [mgKOH / g] (561 ⁇ V) / (W ⁇ S) [However, W: Dispersant sample weighing amount [g], V: Titration determination at the end point of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
  • the amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g.
  • the amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing and titrating the basic amino group with an acid. Dispersibility tends to be good when the amine value is at least the above lower limit value. Further, when the value is not more than the upper limit value, the developability tends to be good.
  • the weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1000 to 200,000, preferably 2000 to 100,000, and more preferably 3000 to 50,000. Especially, 30,000 or less is preferable.
  • Mw weight average molecular weight
  • the value is equal to or higher than the lower limit, the dispersibility and dispersion stability tend to be good. Further, when the value is not more than the upper limit, the solubility tends to be good.
  • the above upper and lower limits can be combined arbitrarily.
  • the alkali developability tends to be good even when the pigment concentration is particularly high.
  • examples of such a particularly preferable commercially available urethane dispersant include Disperbyk 167 and 182 (Big Chemie).
  • the content ratio of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. It is 20% by mass or less, usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 50% by mass is preferable, 3 to 50% by mass is more preferable, 5 to 30% by mass is further preferable, 7 to 30% by mass is further preferable, and 10 to 20% by mass is particularly preferable.
  • the content ratio of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less with respect to 100 parts by mass of the (D) coloring material. It is preferably 80 parts by mass or less, more preferably 50 parts by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 to 200 parts by mass is preferable, 10 to 80 parts by mass is more preferable, and 15 to 50 parts by mass is further preferable.
  • the value is equal to or higher than the lower limit, it tends to be easy to secure sufficient dispersibility. Further, when the value is not more than the upper limit, the color density, sensitivity, film forming property and the like tend to be sufficient without reducing the ratio of other components.
  • the photosensitive resin composition in the present invention preferably contains thiols in order to increase the sensitivity and the adhesion to the substrate.
  • thiols include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylolpropane tristhio.
  • Polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferable, and among them, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are more preferable, and Karenz MT PE1 is particularly preferable.
  • the content ratio of the thiol compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably, with respect to the total solid content of the photosensitive resin composition in the present invention. Is 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less.
  • the value By setting the value to the lower limit or more, there is a tendency that the decrease in sensitivity can be suppressed. Further, when the value is not more than the upper limit, the storage stability tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.3 to 10% by mass is more preferable, and 0.5 to 5% by mass is further preferable.
  • the photosensitive resin composition in the present invention usually contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and (D) a coloring material used as necessary.
  • Various materials are used in a state of being dissolved or dispersed in an organic solvent.
  • the organic solvent used in the production method of the present invention or the organic solvent contained in the carboxy group-containing resin-containing liquid of the present invention may be used as it is.
  • the organic solvent it is preferable to select a solvent having a boiling point (pressure 1013.25 [hPa] condition; hereinafter, the same applies to all boiling points) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C. Examples of such an organic solvent include the following.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Glycol monoalkyl ethers such as monoethyl ether, tripropylene glycol methyl ether;
  • Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n
  • Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamil ether, ethylisobutyl ether, dihexyl ether; Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl
  • Ketones Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol; Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
  • Aromatic hydrocarbons such as benzene, toluene, xylene, cumene; Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxypropi
  • Halogenated hydrocarbons such as butyl chloride, amilk chloride; Etheretones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile;
  • Examples of commercially available solvents corresponding to the above include mineral spirit, valsol # 2, apco # 18 solvent, apco thinner, and socal solvent No. 1 and No. 2.
  • Solvento # 150 Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (any of them). Also the product name).
  • organic solvents may be used alone or in combination of two or more.
  • glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the composition is relatively high.
  • Glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • Glycol monoalkyl ethers are particularly preferable as other organic solvents that may be used in combination.
  • propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituents in the composition.
  • Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the coloring material tends to aggregate, and the viscosity of the photosensitive resin composition obtained later tends to increase, and the storage stability tends to decrease.
  • the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.
  • an organic solvent having a boiling point of 200 ° C. or higher (hereinafter, may be referred to as "high boiling point solvent”) in combination.
  • high boiling point solvent organic solvent having a boiling point of 200 ° C. or higher
  • the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniformly dispersed state of the coloring material in the composition from being destroyed by rapid drying. .. That is, for example, there is an effect of preventing the generation of foreign matter defects due to precipitation and solidification of coloring materials and the like at the tip of the slit nozzle.
  • dipropylene glycol methyl ether acetate diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, 3-butylene glycol diacetate, triacetin and 1,6-hexanediol diacetate are preferred.
  • the content ratio of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass.
  • the value By setting the value to the lower limit or more, for example, it tends to be possible to prevent the coloring material or the like from precipitating and solidifying at the tip of the slit nozzle to cause foreign matter defects. Further, when the value is not more than the upper limit, the drying temperature of the composition becomes slower, and there is a tendency that problems such as tact defects in the vacuum drying process and pin marks of prebake can be suppressed in the color filter manufacturing process.
  • the content ratio of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more. It is more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less. ..
  • the photosensitive resin composition in the present invention may appropriately contain an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant and the like.
  • an adhesion improver may be contained, and examples thereof include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferable.
  • a silane coupling agent examples include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (manufactured by Shinetsu Silicone Co., Ltd.).
  • Examples thereof include Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning).
  • the silane coupling agent one type may be used, or two or more types may be used in combination in any combination and ratio.
  • an adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, and examples thereof include a phosphoric acid-based adhesion improver and other adhesion improvers.
  • (meth) acryloyloxy group-containing phosphates are preferable, and among them, those represented by the following general formulas (g1), (g2) and (g3) are preferable.
  • R 51 independently represents a hydrogen atom or a methyl group
  • m is independently 1. 2 or 3.
  • adhesion improvers include TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesives may be used alone or in combination of two or more.
  • the content ratio of the adhesion improver in the photosensitive resin composition is not particularly limited, but 0.01 in the total solid content in the photosensitive resin composition.
  • mass or more 0.1% by mass or more is more preferable, 0.5% by mass or more is further preferable, 5% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is further preferable. , 1.5% by mass or less is particularly preferable.
  • the value is equal to or higher than the lower limit, the adhesion tends to be improved. Further, when the value is not more than the upper limit value, the developability tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.01 to 3% by mass is more preferable, 0.1 to 2% by mass is further preferable, and 0.5 to 1.5% by mass is particularly preferable.
  • the photosensitive resin composition in the present invention may contain a surfactant as a coatability improver in order to improve the coatability.
  • a surfactant for example, anionic, cationic, nonionic and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicone-based surfactant is effective in terms of coatability.
  • surfactants examples include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340. (Manufactured by Shinetsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nippon Unicar) and FC4430 (manufactured by 3M Japan).
  • the surfactant one type may be used, or two or more types may be used in combination in any combination and ratio.
  • the content ratio of the surfactant in the photosensitive resin composition is not particularly limited, but 0.01 in the total solid content in the photosensitive resin composition.
  • mass or more is preferable, 0.05% by mass or more is more preferable, 1.0% by mass or less is preferable, 0.7% by mass or less is more preferable, 0.5% by mass or less is further preferable, and 0.3 by mass. Mass% or less is particularly preferable.
  • the value is equal to or higher than the lower limit, the resist coating uniformity tends to be improved.
  • the resist sensitivity tends not to decrease.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferable, 0.01 to 0.7% by mass is more preferable, 0.05 to 0.5% by mass is further preferable, and 0.05 to 0.3% by mass is preferable. Especially preferable.
  • the photosensitive resin composition in the present invention may contain a pigment derivative in order to improve dispersibility and storage stability.
  • Pigment derivatives include, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, perinone-based, and diketopyrrolopyrrole-based.
  • Dioxazine-based derivatives among which phthalocyanine-based and quinophthalone-based derivatives are preferable.
  • a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group and the like are directly on the pigment skeleton or an alkyl group, an aryl group or a complex. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton.
  • the pigment derivative examples include phthalocyanine sulfonic acid derivative, quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, quinacridone sulfonic acid derivative, diketopyrrolopyrrole sulfonic acid derivative, and dioxazine sulfonic acid derivative. These may be used alone or in combination of two or more.
  • the blending ratio of the pigment derivative is not particularly limited, but is preferably 0.1% by mass or more with respect to the total solid content of the photosensitive resin composition. 5% by mass or more is more preferable, 1.0% by mass or more is further preferable, 10% by mass or less is preferable, and 5% by mass or less is more preferable.
  • the value is equal to or higher than the lower limit, the dispersion stability tends to be improved. Further, when the value is not more than the upper limit value, the developability tends to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1.0 to 5% by mass is further preferable.
  • the photosensitive resin composition in the present invention can be suitably used for forming a black matrix, and from such a viewpoint, it is preferably black.
  • the optical density (OD) per 1 ⁇ m of the coating film is preferably 1.0 or more, more preferably 2.0 or more, further preferably 2.5 or more, still more preferably 3.0 or more, and 4 9.0 or more is particularly preferable, 4.5 or more is most preferable, and usually 6.0 or less, for example, 1.0 to 6.0 is preferable, 2.0 to 6.0 is more preferable, and 2.5 to 6.0. 6.0 is even more preferred, 3.0 to 6.0 is even more preferred, 4.0 to 6.0 is particularly preferred, and 4.5 to 6.0 is most preferred.
  • 4.0 to 6.0 is particularly preferred, and 4.5 to 6.0 is most preferred.
  • the method for producing a photosensitive resin composition of the present invention is a method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator.
  • A) The alkali-soluble resin includes a carboxy group-containing resin-containing liquid produced by the production method of the present invention.
  • the photosensitive resin composition produced by the production method of the present invention may contain (D) a coloring material.
  • the photosensitive resin composition in the present invention is produced, for example, by the following method.
  • the (D) coloring material is previously dispersed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. It is preferable to do so. Since the (D) coloring material is made into fine particles by the dispersion treatment, the coating characteristics of the resist are improved. Further, when a black color material is used as the (D) color material, it contributes to the improvement of the light-shielding ability.
  • the dispersion treatment is preferably carried out in a system in which (D) a coloring material, an organic solvent, and if necessary, a dispersant and (A) a part or all of an alkali-soluble resin are used in combination.
  • a coloring material e.g., a coloring material, an organic solvent, and if necessary, a dispersant and (A) a part or all of an alkali-soluble resin are used in combination.
  • the mixture to be subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as "ink” or "pigment dispersion liquid".
  • a polymer dispersant is used as the dispersant, it is obtained. It is preferable because the thickening of the ink and the resist over time is suppressed (excellent in dispersion stability).
  • the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
  • the (D) coloring material is dispersed with a sand grinder
  • glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used.
  • the dispersion treatment conditions are such that the temperature is usually 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C.
  • the dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment device, etc., and is appropriately adjusted.
  • the guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the resist is in the range of 100 to 200.
  • the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, etc. .. Further, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
  • the components contained in the photosensitive resin composition that is, (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and (D) a coloring material are contained, the above
  • the ink or the like obtained by the dispersion treatment is blended and mixed at a temperature of 20 to 30 ° C. to obtain a uniform solution.
  • fine dust is often mixed in the liquid, so it is desirable to filter the obtained resist with a filter or the like.
  • the method for producing an ink of the present invention is a method for producing an ink containing (A) an alkali-soluble resin, an organic solvent and (D) a coloring material, and is produced as (A) an alkali-soluble resin by the production method of the present invention. Includes blending a carboxy group-containing resin-containing liquid. A dispersant may be added to the ink, if necessary. Further, the ink of the present invention contains (A) an alkali-soluble resin, an organic solvent and (D) a coloring material, and the (A) alkali-soluble resin contains a carboxy group derived from the carboxy group-containing resin-containing liquid of the present invention. Contains resin.
  • the ink of the present invention may contain a dispersant, if necessary.
  • the ink produced by the method for producing an ink of the present invention and the ink of the present invention are collectively referred to as "ink in the present invention".
  • the organic solvent, (D) coloring material and dispersant those used in the photosensitive resin composition can be preferably used.
  • the ink in the present invention can be obtained, for example, by the dispersion treatment described in the method for producing a photosensitive resin composition.
  • the method for producing a cured product of the present invention includes curing the photosensitive resin composition obtained by the production method of the present invention. Further, the cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention.
  • the cured product obtained by curing the photosensitive resin composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix or a colored spacer.
  • the method for producing a black matrix of the present invention includes forming a black matrix using the cured product obtained by the production method of the present invention. Further, the black matrix of the present invention is formed by using the photosensitive resin composition of the present invention. The cured product obtained by the production method of the present invention or the black matrix using the cured product of the present invention will be described according to the production method.
  • the material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength.
  • a transparent substrate is mainly used, and as the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy resin.
  • a heat-curable resin sheet such as unsaturated polyester resin and poly (meth) acrylic resin, and various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance.
  • a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. Other than the transparent substrate, it can be formed on, for example, a TFT array.
  • the support is subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, and thin film formation treatment of various resins such as urethane resin, if necessary. You may go.
  • the thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm.
  • the film thickness is usually in the range of 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
  • the photosensitive resin composition obtained by the production method of the present invention or the present invention is used.
  • Examples thereof include a method of forming a black matrix with a cured product obtained by curing the photosensitive resin composition of the above.
  • a photomask is placed on a dried sample, and image exposure, development, heat curing or light as necessary is performed through the photomask.
  • the thickness of the coating film is usually preferably in the range of 0.2 to 10 ⁇ m, more preferably in the range of 0.5 to 6 ⁇ m, and further preferably in the range of 1 to 4 ⁇ m as the film thickness after drying. be.
  • Drying of coating film Drying of the coating film after applying the photosensitive resin composition to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven.
  • the drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer used, and the like.
  • the drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.
  • the step of drying the coating film may be a vacuum drying method in which the coating film is dried in a reduced pressure chamber without raising the temperature.
  • Exposure Image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive resin composition and irradiating light having a wavelength from the ultraviolet region to the visible region through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film.
  • the light source used for the above image exposure is not particularly limited.
  • the light source examples include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a carbon arc.
  • a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a carbon arc.
  • An optical filter can also be used when irradiating light of a specific wavelength for use.
  • a coating film made of a photosensitive resin composition is subjected to image exposure with the above-mentioned light source, and then an organic solvent or an aqueous solution containing a surfactant and an alkaline compound is used. Depending on the development used, an image can be formed and produced on the substrate.
  • the aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
  • alkaline compound examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus.
  • Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- Or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc.
  • Examples include organic alkaline compounds. These alkaline compounds may be used alone or as a mixture of two or more.
  • the surfactant examples include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids.
  • anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts
  • amphoteric surfactants such as alkyl betaines and amino acids.
  • the organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol.
  • the organic solvent may be used alone or in combination with an aqueous solution.
  • the conditions of the development process are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly preferably 15 to 45 ° C., particularly preferably 20 to 40 ° C., and the development methods are a dip development method, a spray development method, and a brush. Any method such as a developing method or an ultrasonic developing method can be used.
  • thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment.
  • the thermosetting treatment conditions at this time are selected in the range of 100 to 280 ° C., preferably 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.
  • the height of the black matrix formed as described above is usually 0.5 to 5 ⁇ m, preferably 0.8 to 4 ⁇ m.
  • the optical density (OD) per 1 ⁇ m of thickness is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.2 or more.
  • a photosensitive resin composition containing one of red, green, and blue coloring materials is applied onto a transparent substrate provided with a black matrix by the same process as in (3-1) to (3-5) above, and dried. After that, a photomask is superposed on the coating film, and a pixel image is formed through the photomask by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer.
  • a color filter can be formed by performing this operation on each of the three color photosensitive resin compositions of red, green, and blue. These orders are not limited to the above.
  • the photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention can also be used as a resist for a colored spacer in addition to the black matrix.
  • the spacer is used for the TFT type LCD, the TFT may malfunction as a switching element due to the light incident on the TFT, and the colored spacer is used to prevent this.
  • Japanese Patent Application Laid-Open No. 8-234212 The publication describes that the spacer has a light-shielding property.
  • the colored spacer can be formed by the same method as the above-mentioned black matrix except that a mask for the colored spacer is used.
  • a color filter forms a transparent electrode such as ITO on an image in this state and is used as a part of parts such as a color display and a liquid crystal display device, but the surface is smooth. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image in order to improve the properties and durability. Further, in some applications such as a plane alignment type drive system (IPS mode), a transparent electrode may not be formed.
  • IPS mode plane alignment type drive system
  • the photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention can also be used to form a partition wall, particularly a partition wall for partitioning an organic layer of an organic electric field light emitting element.
  • a partition wall for partitioning an organic layer of an organic electric field light emitting element.
  • the organic layer used for the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396. Examples include the organic layer used.
  • the photosensitive resin composition obtained by the production method of the present invention or the partition wall using the photosensitive resin composition of the present invention will be described according to the production method.
  • the photosensitive resin composition is supplied in the form of a film or a pattern on a substrate on which a partition wall should be provided by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method that performs exposure-development. After that, a partition wall is formed on the substrate by performing additional exposure and thermosetting treatment as necessary.
  • the size and shape of the partition wall when used as a partition wall are appropriately adjusted depending on the specifications of the organic electroluminescent device to which the partition wall is applied, but the height of the partition wall formed from the photosensitive resin composition is usually 0.5 to 10 ⁇ m. Degree.
  • the organic electroluminescent device of the present invention comprises a cured product of the present invention, for example, a partition wall.
  • various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the above method.
  • the method for forming the organic electric field light emitting device is not particularly limited, but preferably, after forming the pattern of the partition wall on the substrate by the above-mentioned method, the functional material is sublimated in a vacuum state and the region surrounded by the partition wall on the substrate.
  • An organic electric field light emitting device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method in which a film is formed by adhering to the inside, a casting method, a spin coating method, or an inkjet printing method.
  • Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
  • a partition wall is formed on a glass substrate on which transparent electrodes are laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall.
  • a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall. Is created.
  • Examples of the light emitting layer include an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
  • each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency.
  • the thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.
  • the organic electroluminescent element may be formed by separating each RGB color for each opening, or two or more colors may be laminated in one opening.
  • the organic electroluminescent device may be provided with a sealing layer from the viewpoint of improving reliability.
  • the sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and lowering the luminous efficiency.
  • the organic electroluminescent device may be provided with a low reflection film at the interface with air from the viewpoint of improving the light extraction efficiency. By arranging the low-reflection film at the interface between the air and the element, it can be expected that the gap in the refractive index is reduced and the reflection at the interface is suppressed. For such a low-reflection film, for example, a technique of a moth-eye structure or a super-multilayer film can be applied.
  • an organic electroluminescent element When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light emitting layer of one pixel from leaking to another pixel, and further, when the electrode or the like is made of metal, it is outside. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to impart light-shielding property to the partition wall constituting the organic electroluminescent element. In an organic electroluminescent device, it is necessary to provide electrodes on the upper surface and the lower surface of the partition wall. Therefore, from the viewpoint of insulating properties, the partition wall preferably has high resistance and low dielectric constant. Therefore, when a colorant is used to impart light-shielding properties to the partition wall, it is preferable to use the organic pigment having high resistance and low dielectric constant.
  • the method for manufacturing an image display device of the present invention is characterized by using a cured product obtained by the manufacturing method of the present invention or a black matrix obtained by the manufacturing method of the present invention. Further, the image display device of the present invention includes the cured product of the present invention or the black matrix of the present invention.
  • the image display device in the present invention has a cured product obtained by curing the photosensitive resin composition in the present invention, and as a method for producing the same, for example, the photosensitive resin composition obtained by the production method in the present invention. Alternatively, a production method using a cured product, a black matrix or a partition wall formed by the photosensitive resin composition of the present invention can be mentioned.
  • the image display device in the present invention is not particularly limited as long as it is a device for displaying an image or a moving image, and examples thereof include a liquid crystal display device and an organic EL display described later.
  • the liquid crystal display device in the present invention has the black matrix in the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.
  • a liquid crystal display device usually forms an alignment film on a color filter, sprays a spacer on the alignment film, attaches the spacer to the facing substrate to form a liquid crystal cell, and injects liquid crystal into the formed liquid crystal cell. It is completed by connecting to the counter electrode.
  • the alignment film a resin film such as polyimide is suitable.
  • a gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.
  • a spacer having a size corresponding to the gap (gap) with the facing substrate is used, and a spacer having a size of 2 to 8 ⁇ m is usually preferable.
  • a photospacer (PS) of a transparent resin film can be formed on a color filter substrate by a photolithography method, and this can be used instead of the spacer.
  • the facing substrate an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.
  • the gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 ⁇ m.
  • the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin.
  • the sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
  • the liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. ..
  • the degree of decompression in the liquid crystal cell is usually 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 -7 Pa, but preferably 1 ⁇ 10 -3 to 1 ⁇ 10 -6 Pa. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The warming retention at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal display.
  • a liquid crystal display device (panel) is completed by sealing the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin and sealing the liquid crystal injection port.
  • the type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a liotropic liquid crystal, a thermotropic liquid crystal, and the like.
  • a thermotropic liquid crystal a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.
  • Organic EL display is manufactured by using the color filter in the present invention and the organic electroluminescent element in the present invention.
  • an organic EL display is manufactured using the color filter of the present invention, for example, as shown in FIG. 1, a pattern formed by a photosensitive resin composition (that is, pixels 20 and adjacent to each other) is first placed on a transparent support substrate 10. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is produced, and an organic illuminant 500 is formed on the color filter via an organic protective layer 30 and an inorganic oxide film 40.
  • the organic EL element 100 can be manufactured by laminating the above. At least one of the pixel 20 and the resin black matrix was produced by using the photosensitive resin composition of the present invention.
  • a method of laminating the organic illuminant 500 a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40.
  • the organic EL element 100 thus produced, for example, the method described in "Organic EL Display” (Ohmsha, August 20, 2004, Luminous, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. , An organic EL display can be manufactured.
  • the color filter in the present invention can be applied to both a passive drive type organic EL display and an active drive type organic EL display.
  • the method for stabilizing the carboxy group-containing resin of the present invention comprises a reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid dianhydride (c). It comprises adding water to a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin obtained by reacting the polybasic acid monoanhydride (d) in an organic solvent.
  • the details are the same as in step B in the method for producing the carboxy group-containing resin-containing liquid of the present invention.
  • C) may be obtained by reacting the polybasic acid monoanhydride (d) with the polyhydric alcohol (e) in an organic solvent.
  • the method for producing a carboxy group-containing resin-containing liquid is the same as the above-mentioned type and blending amount.
  • the organic solvent used in the reaction for obtaining the carboxy group-containing resin-containing liquid containing the carboxy group-containing resin the organic solvent used in the method for producing the carboxy group-containing resin-containing liquid of the present invention can be preferably used.
  • the mixture was reacted with stirring at 100 ° C. for 9 hours until the acid value became 5 mgKOH / g or less to obtain an intermediate solution containing an intermediate.
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic acid dianhydride
  • THPA tetrahydrophthalic acid anhydride
  • PGMEA tetrahydrophthalic acid anhydride
  • the polystyrene-equivalent weight average molecular weight (Mw) of the carboxy group-containing resin-containing liquids (1) to (4) obtained in Examples 1 to 3 and Comparative Example 1 and the viscosity of the resin solution were determined by GPC (Watters), respectively. 2695) and a viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd.). The measurement results are shown in Table 1. Further, after storing the carboxy group-containing resin-containing liquids (1) to (4) obtained in Examples 1 to 3 and Comparative Example 1 at 35 ° C. for 14 days, the Mw of each carboxy group-containing resin and the viscosity of the resin solution was measured, and the stability over time was evaluated according to the following criteria. The evaluation results are shown in Table 1.
  • Viscosity change rate (viscosity after storage at 35 ° C. for 14 days) / (viscosity before storage) x 100 (%) ... Equation (II) Evaluation criteria: A: Change rate is less than 150% B: Change rate is 150% or more and less than 200% C: Change rate is 200% or more
  • the weight average molecular weight of the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid is obtained by having the step of adding water to the carboxy group-containing resin-containing liquid. And it can be seen that it is possible to improve the stability of the viscosity over time.
  • water after the synthesis of the carboxy group-containing resin the equilibrium reaction between the carboxy group of the carboxy group-containing resin and the hydroxy group of the carboxy group-containing resin or the polyhydric alcohol is controlled, and the equilibrium reaction is controlled during storage. This is thought to be because the polymerization reaction due to the condensation reaction can be suppressed.

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Abstract

Provided are a method for producing a carboxy-group-containing resin-containing solution having excellent stability over time and a method for stabilizing a carboxy-group-containing resin. The method for producing a carboxy-group-containing resin-containing solution of the present invention is characterized by including a step A for reacting a reaction intermediate obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid anhydride (d) and synthesizing a first carboxy-group-containing resin-containing solution and a step B for adding water to the first carboxy-group-containing resin-containing solution to obtain a second carboxy-group-containing resin-containing solution.

Description

カルボキシ基含有樹脂含有液の製造方法及びカルボキシ基含有樹脂の安定化方法Method for producing carboxy group-containing resin-containing liquid and method for stabilizing carboxy group-containing resin
　本発明は、カルボキシ基含有樹脂含有液の製造方法、インクの製造方法、感光性樹脂組成物の製造方法、硬化物の製造方法、ブラックマトリックス（Ｂｌａｃｋ　Ｍａｔｒｉｘ）の製造方法、画像表示装置の製造方法、カルボキシ含有樹脂含有液、インク、感光性樹脂組成物、硬化物、ブラックマトリックス、画像表示装置、カルボキシ基含有樹脂の安定化方法に関する。
　本願は、２０２０年１０月３０日に日本に出願された特願２０２０－１８２９８３号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a method for producing a carboxy group-containing resin-containing liquid, a method for producing ink, a method for producing a photosensitive resin composition, a method for producing a cured product, a method for producing a black matrix, and a method for producing an image display device. , A carboxy-containing resin-containing liquid, an ink, a photosensitive resin composition, a cured product, a black matrix, an image display device, and a method for stabilizing a carboxy group-containing resin.
This application claims priority based on Japanese Patent Application No. 2020-182983 filed in Japan on October 30, 2020, the contents of which are incorporated herein by reference.
　カラーフィルターは、通常、ガラス、プラスチック等の透明基板の表面に、黒色のブラックマトリックスを形成し、続いて、赤、緑、青等の３種以上の異なる色の画素を順次、格子状、ストライプ状またはモザイク状等のパターンで形成したものである。パターンサイズはカラーフィルターの用途並びにそれぞれの色により異なるが通常５～７００μｍ程度である。 A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic, and then sequentially grids and stripes pixels of three or more different colors such as red, green, and blue. It is formed by a pattern such as a shape or a mosaic shape. The pattern size varies depending on the use of the color filter and each color, but is usually about 5 to 700 μm.
　カラーフィルターの代表的な製造方法として、現在、感光性樹脂組成物を用いたフォトリソグラフィー法が知られている。フォトリソグラフィーによりカラーフィルターを製造する場合、まずアルカリ現像可能なカルボキシ基含有樹脂を含む感光性樹脂組成物を透明基板上に塗布した後に乾燥させ、さらに画像露光、アルカリ現像液を用いて現像した後、２００℃以上の高温処理により硬化（キュア）させることでパターンを形成するが、このような感光性樹脂組成物は、カルボキシ基含有樹脂の分子量や粘度によって、線幅や膜厚が変化するため、カルボキシ基含有樹脂の経時安定性が低いとカラーフィルターの歩留まり低下等の問題が生じていた。 Currently, a photolithography method using a photosensitive resin composition is known as a typical manufacturing method of a color filter. When a color filter is manufactured by photolithography, a photosensitive resin composition containing a carboxy group-containing resin capable of alkaline development is first applied onto a transparent substrate, dried, and then developed using image exposure and an alkaline developer. A pattern is formed by curing by high-temperature treatment at 200 ° C. or higher. However, in such a photosensitive resin composition, the line width and film thickness change depending on the molecular weight and viscosity of the carboxy group-containing resin. If the stability of the carboxy group-containing resin over time is low, problems such as a decrease in the yield of the color filter have occurred.
　こうした背景から、カルボキシ基含有樹脂を安定的に製造する方法が求められている。例えば、特許文献１～２には特定の条件を用いたカルボキシ基含有樹脂の製造方法が記載されている。 Against this background, there is a demand for a method for stably producing a carboxy group-containing resin. For example, Patent Documents 1 and 2 describe a method for producing a carboxy group-containing resin using specific conditions.
日本国特開２０００－３３６１１６号公報Japanese Patent Application Laid-Open No. 2000-336116 日本国特開２００５－４１９５８号公報Japanese Patent Application Laid-Open No. 2005-41958
　本発明者らが、特許文献１～２に記載の製造法を用いてカルボキシ基含有樹脂を製造したところ、経時安定性が十分ではないことが分かった。 When the present inventors produced a carboxy group-containing resin by using the production methods described in Patent Documents 1 and 2, it was found that the stability over time was not sufficient.
　そこで本発明は、経時安定性に優れたカルボキシ基含有樹脂含有液の製造方法及びカルボキシ基含有樹脂の安定化方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing a carboxy group-containing resin-containing liquid having excellent stability over time and a method for stabilizing the carboxy group-containing resin.
　本発明者らは前記課題を解決すべく鋭意検討した結果、特定の方法を用いてカルボキシ基含有樹脂含有液を製造することにより、前記課題を解決できることを見出した。即ち本発明の要旨は以下に存する。 As a result of diligent studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by producing a carboxy group-containing resin-containing liquid using a specific method. That is, the gist of the present invention lies below.
［１］エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させ、第一のカルボキシ基含有樹脂含有液を得る工程Ａと、
　前記第一のカルボキシ基含有樹脂含有液に水を添加して、第二のカルボキシ基含有樹脂含有液を得る工程Ｂとを含む、カルボキシ基含有樹脂含有液の製造方法。
［２］前記第二のカルボキシ基含有樹脂含有液の含有水分率が０．１質量％以上になるように、前記第一のカルボキシ基含有樹脂含有液に水を添加する、［１］に記載のカルボキシ基含有樹脂含有液の製造方法。
［３］前記工程Ａにおいて、さらに多価アルコール（ｅ）を加えて反応させる、［１］又は［２］に記載のカルボキシ基含有樹脂含有液の製造方法。
［４］前記多価アルコール（ｅ）が、トリメチロールプロパンを含む、［３］に記載のカルボキシ基含有樹脂含有液の製造方法。
［５］前記多塩基酸二無水物（ｃ）が、ビフェニルテトラカルボン酸二無水物を含む、［１］～［４］のいずれかに記載のカルボキシ基含有樹脂含有液の製造方法。
［６］前記多塩基酸一無水物（ｄ）が、テトラヒドロフタル酸無水物を含む、［１］～［５］のいずれかに記載のカルボキシ基含有樹脂含有液の製造方法。
［７］（Ａ）アルカリ可溶性樹脂、有機溶媒及び（Ｄ）色材を含むインクの製造方法であって、
　前記（Ａ）アルカリ可溶性樹脂として、［１］～［６］のいずれかに記載の製造方法で製造されたカルボキシ基含有樹脂含有液を配合することを含む、インクの製造方法。
［８］（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤を含む感光性樹脂組成物の製造方法であって、
　前記（Ａ）アルカリ可溶性樹脂として、［１］～［６］のいずれかに記載の製造方法で製造されたカルボキシ基含有樹脂含有液を配合することを含む、感光性樹脂組成物の製造方法。
［９］前記感光性樹脂組成物が、さらに（Ｄ）色材を含む、［８］に記載の感光性樹脂組成物の製造方法。
［１０］［８］又は［９］に記載の製造方法で得られた感光性樹脂組成物を硬化させることを含む、硬化物の製造方法。
［１１］［１０］に記載の製造方法で得られた硬化物を用いてブラックマトリックスを形成することを含む、ブラックマトリックスの製造方法。
［１２］［１０］に記載の製造方法で得られた硬化物、又は［１１］に記載の製造方法で得られたブラックマトリックスを用いることを特徴とする、画像表示装置の製造方法。
［１３］カルボキシ基含有樹脂、有機溶媒及び水を含有し、含有水分率が０．１質量％以上１質量％以下である、カルボキシ基含有樹脂含有液。
［１４］前記カルボキシ基含有樹脂がエポキシ化合物（ａ）由来の構造を有する［１３］に記載のカルボキシ基含有樹脂含有液。
［１５］前記カルボキシ基含有樹脂が不飽和一塩基酸（ｂ）由来の構造を有する［１３］又は［１４］に記載のカルボキシ基含有樹脂含有液。
［１６］前記カルボキシ基含有樹脂が多塩基酸二無水物（ｃ）由来の構造を有する［１３］～［１５］のいずれかに記載のカルボキシ基含有樹脂含有液。
［１７］前記カルボキシ基含有樹脂が多塩基酸一無水物（ｄ）由来の構造を有する［１３］～［１６］のいずれかに記載のカルボキシ基含有樹脂含有液。
［１８］（Ａ）アルカリ可溶性樹脂、有機溶媒及び（Ｄ）色材を含有し、
　前記（Ａ）アルカリ可溶性樹脂が、［１３］～［１７］のいずれかに記載のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含むインク。
［１９］（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤を含有し、
　前記（Ａ）アルカリ可溶性樹脂が、［１３］～［１７］のいずれかに記載のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含む感光性樹脂組成物。
［２０］［１９］に記載の感光性樹脂組成物を硬化してなる硬化物。
［２１］［２０］に記載の硬化物を用いて形成されてなるブラックマトリックス。
［２２］［２０］に記載の硬化物、又は［２１］に記載のブラックマトリックスを備える、画像表示装置。
［２３］エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させて得られる、カルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液に、水を添加することを含む、カルボキシ基含有樹脂の安定化方法。
［２４］水を添加した後のカルボキシ基含有樹脂含有液の含有水分率が０．１質量％以上になるように水を添加する、［２３］に記載のカルボキシ基含有樹脂の安定化方法。
［２５］前記カルボキシ基含有樹脂含有液が、前記エポキシ化合物（ａ）と前記不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、前記多塩基酸二無水物（ｃ）と、前記多塩基酸一無水物（ｄ）と、多価アルコール（ｅ）とを有機溶媒中で反応させて得られるカルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液である、［２３］又は［２４］に記載のカルボキシ基含有樹脂の安定化方法。
［２６］前記多価アルコール（ｅ）が、トリメチロールプロパンを含む、［２５］に記載のカルボキシ基含有樹脂の安定化方法。
［２７］前記多塩基酸二無水物（ｃ）が、ビフェニルテトラカルボン酸二無水物を含む、［２３］～［２６］のいずれかに記載のカルボキシ基含有樹脂の安定化方法。
［２８］前記多塩基酸一無水物（ｄ）が、テトラヒドロフタル酸無水物を含む、［２３］～［２７］のいずれかに記載のカルボキシ基含有樹脂の安定化方法。 [1] A reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d). In step A to obtain the first carboxy group-containing resin-containing liquid by reacting in an organic solvent.
A method for producing a carboxy group-containing resin-containing liquid, which comprises the step B of adding water to the first carboxy group-containing resin-containing liquid to obtain a second carboxy group-containing resin-containing liquid.
[2] The description in [1], wherein water is added to the first carboxy group-containing resin-containing liquid so that the water content of the second carboxy group-containing resin-containing liquid is 0.1% by mass or more. A method for producing a carboxy group-containing resin-containing liquid.
[3] The method for producing a carboxy group-containing resin-containing liquid according to [1] or [2], wherein the polyhydric alcohol (e) is further added and reacted in the step A.
[4] The method for producing a carboxy group-containing resin-containing liquid according to [3], wherein the polyhydric alcohol (e) contains trimethylolpropane.
[5] The method for producing a carboxy group-containing resin-containing liquid according to any one of [1] to [4], wherein the polybasic acid dianhydride (c) contains a biphenyltetracarboxylic acid dianhydride.
[6] The method for producing a carboxy group-containing resin-containing liquid according to any one of [1] to [5], wherein the polybasic acid monoanhydride (d) contains a tetrahydrophthalic anhydride.
[7] A method for producing an ink containing (A) an alkali-soluble resin, an organic solvent, and (D) a coloring material.
A method for producing an ink, which comprises blending the carboxy group-containing resin-containing liquid produced by the production method according to any one of [1] to [6] as the alkali-soluble resin (A).
[8] A method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator.
A method for producing a photosensitive resin composition, which comprises blending the carboxy group-containing resin-containing liquid produced by the production method according to any one of [1] to [6] as the alkali-soluble resin (A).
[9] The method for producing a photosensitive resin composition according to [8], wherein the photosensitive resin composition further contains (D) a coloring material.
[10] A method for producing a cured product, which comprises curing the photosensitive resin composition obtained by the production method according to [10] [8] or [9].
[11] A method for producing a black matrix, which comprises forming a black matrix using the cured product obtained by the production method according to [10].
[12] A method for manufacturing an image display device, which comprises using the cured product obtained by the manufacturing method according to [10] or the black matrix obtained by the manufacturing method according to [11].
[13] A carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, an organic solvent and water, and having a water content of 0.1% by mass or more and 1% by mass or less.
[14] The carboxy group-containing resin-containing liquid according to [13], wherein the carboxy group-containing resin has a structure derived from the epoxy compound (a).
[15] The carboxy group-containing resin-containing liquid according to [13] or [14], wherein the carboxy group-containing resin has a structure derived from the unsaturated monobasic acid (b).
[16] The carboxy group-containing resin-containing liquid according to any one of [13] to [15], wherein the carboxy group-containing resin has a structure derived from the polybasic acid dianhydride (c).
[17] The carboxy group-containing resin-containing liquid according to any one of [13] to [16], wherein the carboxy group-containing resin has a structure derived from the polybasic acid monoanhydride (d).
[18] Containing (A) an alkali-soluble resin, an organic solvent and (D) a coloring material,
An ink in which the alkali-soluble resin (A) contains a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid according to any one of [13] to [17].
[19] Containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator,
A photosensitive resin composition in which the alkali-soluble resin (A) contains a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid according to any one of [13] to [17].
[20] A cured product obtained by curing the photosensitive resin composition according to [19].
[21] A black matrix formed by using the cured product according to [20].
[22] An image display device comprising the cured product according to [20] or the black matrix according to [21].
[23] A reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d). A method for stabilizing a carboxy group-containing resin, which comprises adding water to a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, which is obtained by reacting the above in an organic solvent.
[24] The method for stabilizing a carboxy group-containing resin according to [23], wherein water is added so that the water content of the carboxy group-containing resin-containing liquid after the addition of water is 0.1% by mass or more.
[25] The reaction product obtained by reacting the epoxy compound (a) with the unsaturated monobasic acid (b) and the polybasic acid dianhydride (c) by the carboxy group-containing resin-containing liquid. [23] or a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin obtained by reacting the polybasic acid monoanhydride (d) with the polyhydric alcohol (e) in an organic solvent. [24] The method for stabilizing a carboxy group-containing resin according to [24].
[26] The method for stabilizing a carboxy group-containing resin according to [25], wherein the polyhydric alcohol (e) contains trimethylolpropane.
[27] The method for stabilizing a carboxy group-containing resin according to any one of [23] to [26], wherein the polybasic acid dianhydride (c) contains a biphenyltetracarboxylic acid dianhydride.
[28] The method for stabilizing a carboxy group-containing resin according to any one of [23] to [27], wherein the polybasic acid monoanhydride (d) contains a tetrahydrophthalic anhydride.
　本発明によれば、経時安定性に優れたカルボキシ基含有樹脂の製造方法及びカルボキシ基含有樹脂の安定化方法を提供することができる。 According to the present invention, it is possible to provide a method for producing a carboxy group-containing resin having excellent stability over time and a method for stabilizing the carboxy group-containing resin.
本発明におけるカラーフィルターを備えた有機ＥＬ素子の一例を示す断面概略図である。It is sectional drawing which shows an example of the organic EL element provided with the color filter in this invention.
　以下、本発明の実施の形態を具体的に説明するが、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々に変更して実施することができる。
　なお、本発明において、「（メタ）アクリル」とは「アクリル及び／又はメタクリル」を意味し、「（メタ）アクリレート」、「（メタ）アクリロイル」についても同様である。 Hereinafter, embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and the same applies to "(meth) acrylate" and "(meth) acryloyl".
　本発明において「全固形分」とは、感光性樹脂組成物中又は後述するインク中に含まれる、有機溶媒及び水以外の全成分を意味するものとする。
　本発明において「感光性樹脂組成物」を「レジスト」と称することがある。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）を指す。
　本発明において、「アミン価」とは、特に断りのない限り、有効固形分換算のアミン価を表し、分散剤の固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表される値である。なお、測定方法については後述する。 In the present invention, the "total solid content" means all the components other than the organic solvent and water contained in the photosensitive resin composition or the ink described later.
In the present invention, the "photosensitive resin composition" may be referred to as "resist".
In the present invention, the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the "amine value" represents an amine value in terms of effective solid content, and is a value represented by the amount of base per 1 g of solid content of the dispersant and the equivalent mass of KOH, unless otherwise specified. .. The measurement method will be described later.
［カルボキシ基含有樹脂含有液の製造方法］
　本発明のカルボキシ基含有樹脂含有液の製造方法は、エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させ、カルボキシ基含有樹脂含有液（「第一のカルボキシ基含有樹脂含有液」とも言う。）を得る工程Ａと、前記工程Ａで得られたカルボキシ基含有樹脂含有液（第一のカルボキシ基含有樹脂含有液）に水を添加して、水が添加されたカルボキシ基含有樹脂含有液（「第二のカルボキシ基含有樹脂含有液」とも言う。）を得る工程Ｂを有する。
　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物はカルボキシ基含有樹脂の中間体とも言えるため、以下、「中間体」と称する場合がある。
　カルボキシ基含有樹脂含有液は、カルボキシ基含有樹脂を含む液状混合物であれば、懸濁液、分散液又は溶液であってよく、カルボキシ基含有樹脂含有溶液であることが好ましい。 [Manufacturing method of carboxy group-containing resin-containing liquid]
The method for producing a carboxy group-containing resin-containing liquid of the present invention comprises a reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), and a polybasic acid dianhydride (c). , The step A of reacting the polybasic acid monoanhydride (d) in an organic solvent to obtain a carboxy group-containing resin-containing liquid (also referred to as “first carboxy group-containing resin-containing liquid”), and the above-mentioned step A. Water was added to the carboxy group-containing resin-containing liquid (first carboxy group-containing resin-containing liquid) obtained in the above step, and water was added to the carboxy group-containing resin-containing liquid (“second carboxy group-containing resin-containing liquid). It also has a step B for obtaining).
Since the reaction product obtained by reacting the epoxy compound (a) with the unsaturated monobasic acid (b) can be said to be an intermediate of the carboxy group-containing resin, it may be referred to as an "intermediate" below.
The carboxy group-containing resin-containing liquid may be a suspension, a dispersion liquid or a solution as long as it is a liquid mixture containing a carboxy group-containing resin, and is preferably a carboxy group-containing resin-containing solution.
＜工程Ａ＞
　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られた反応生成物（中間体）と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させ、第一のカルボキシ基含有樹脂を得る工程である。 <Process A>
A reaction product (intermediate) obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d). ) In an organic solvent to obtain the first carboxy group-containing resin.
　エポキシ化合物（ａ）としては、エポキシ基を有する化合物であれば、特に限定されない。例えば、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標。以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」等）、ビスフェノールＡ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ（例えば、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃））、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ＥＰ－４００１」、「ＥＰ－４００２」、「ＥＰ－４００４等」）、ビスフェノールＦ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ樹脂（例えば、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃））、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－２０１」、三菱ケミカル社製の「ＥＰ－１５２」、「ＥＰ－１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標。以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標。以下同じ。）－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標。以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、エポキシ基含有（メタ）アクリレートと他のラジカル重合性単量体との共重合体、下記一般式（ａ１）～（ａ６）で表されるエポキシ化合物を好適に用いることができる。
　具体的には、例えば、下記一般式（ａ１）で表されるエポキシ化合物として日本化薬社製の「ＸＤ－１０００」、下記一般式（ａ２）で表されるエポキシ化合物として日本化薬社製の「ＮＣ－３０００」、下記一般式（ａ４）で表されるエポキシ化合物として新日鐵住金化学社製の「ＥＳＦ－３００」が挙げられる。 The epoxy compound (a) is not particularly limited as long as it is a compound having an epoxy group. For example, bisphenol A type epoxy resin (for example, "jER (registered trademark. The same shall apply hereinafter) 828", "jER1001", "jER1002", "jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, alcoholic properties of bisphenol A type epoxy resin. Epoxy obtained by the reaction of hydroxyl group and epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323, softening point 76 ° C.)), bisphenol F type resin (for example, "jER807" manufactured by Mitsubishi Chemical Corporation). , "EP-4001", "EP-4002", "EP-4004, etc."), an epoxy resin obtained by the reaction of the alcoholic hydroxyl group of the bisphenol F type epoxy resin with epichlorohydrin (for example, "NER" manufactured by Nippon Kayaku Co., Ltd. -7406 "(epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example," YX-4000 "manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy resin (for example, Nippon Kayaku). "EPPN-201" manufactured by Mitsubishi Chemical Corporation, "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (o, m, p-) Cresol novolac type epoxy Resin (for example, "EOCN (registered trademark; the same applies hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., and triglycidyl isocyanurate (for example, "EOCN-104S" manufactured by Nissan Chemical Corporation. TEPIC®) ”), Trisphenol methane type epoxy resin (for example,“ EPPN (registered trademark; the same shall apply hereinafter) -501 ”,“ EPPN-502 ”,“ EPPN-503 ”) manufactured by Nippon Kayaku Co., Ltd., Alicyclic epoxy resin (“Selokiside (registered trademark; the same applies hereinafter) 2021P” manufactured by Daicel Co., Ltd., “Selokiside EHPE”), an epoxy resin obtained by glycidylizing a phenol resin produced by the reaction of dicyclopentadiene and phenol (for example, DIC Co., Ltd.) "EXA-7200" manufactured by Nippon Kayaku Co., Ltd., "NC-7300" manufactured by Nippon Kayaku Co., Ltd., a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, the following general formula (a1) to The epoxy compound represented by (a6) can be preferably used.
Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. as an epoxy compound represented by the following general formula (a1), and Nippon Kayaku Co., Ltd. as an epoxy compound represented by the following general formula (a2). "NC-3000" and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Corporation can be mentioned as an epoxy compound represented by the following general formula (a4).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　上記一般式（ａ１）において、ｂ１１は平均値を示し、０～１０の数を示す。Ｒ11は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ11は互いに同一であっても異なっていてもよい。 In the above general formula (a1), b11 indicates an average value and indicates a number from 0 to 10. R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 11s existing in one molecule may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　上記一般式（ａ２）において、ｂ１２は平均値を示し、０～１０の数を示す。Ｒ21は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ21は互いに同一であっても異なっていてもよい。 In the above general formula (a2), b12 indicates an average value and indicates a number from 0 to 10. R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 21s existing in one molecule may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　上記一般式（ａ３）において、Ｘは下記一般式（ａ３－１）又は（ａ３－２）で表される連結基を示す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｂ１３は２又は３の整数を示す。 In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2). However, the molecular structure contains one or more adamantane structures. b13 indicates an integer of 2 or 3.
　これらの中でも、レジストのパターニング特性の観点からは、Ｘは（ａ３－１）が好ましく、ｂ１３は２が好ましい。 Among these, (a3-1) is preferable for X and 2 is preferable for b13 from the viewpoint of the patterning characteristics of the resist.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　上記一般式（ａ３－１）及び（ａ３－２）において、Ｒ31～Ｒ34及びＲ35～Ｒ37は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を示す。また、式中の＊は式（ａ３）中の結合部位を表す。 In the above general formulas (a3-1) and (a3-2), R 31 to R 34 and R 35 to R 37 each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. Indicates an alkyl group having 1 to 12 carbon atoms which may have an alkyl group, or a phenyl group which may have a substituent. Further, * in the formula represents a binding site in the formula (a3).
　式（ａ３－１）としては、レジストのパターニング特性の観点から、アダマンチル基と水素原子をそれぞれ２つずつ有することが好ましい。式（ａ３－２）としては、レジストのパターニング特性の観点から、アダマンチル基２つと水素原子を１つ有することが好ましい。 The formula (a3-1) preferably has two adamantyl groups and two hydrogen atoms from the viewpoint of the patterning characteristics of the resist. The formula (a3-2) preferably has two adamantyl groups and one hydrogen atom from the viewpoint of the patterning characteristics of the resist.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　上記一般式（ａ４）において、ｐ及びｑは各々独立に０～４の整数を表し、Ｒ41及びＲ42は各々独立に炭素数１～２０のアルキル基又はハロゲン原子を表す。Ｒ43及びＲ44は各々独立に炭素数１～５のアルキレン基を表す。ｘ及びｙはそれぞれ独立して０以上の整数を表す。 In the above general formula (a4), p and q each independently represent an integer of 0 to 4, and R 41 and R 42 each independently represent an alkyl group or a halogen atom having 1 to 20 carbon atoms. R 43 and R 44 each independently represent an alkylene group having 1 to 5 carbon atoms. x and y each independently represent an integer of 0 or more.
　これらの中でも、レジストのパターニング特性の観点からは、ｐ、ｑ、ｘ、及びｙは０が好ましい。 Among these, 0 is preferable for p, q, x, and y from the viewpoint of the patterning characteristics of the resist.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　上記一般式（ａ５）において、Ｒ51～Ｒ54は各々独立に、水素原子、炭素数１～２０のアルキル基、炭素原子６～２０のアリール基、又は、炭素原子７～２０のアラルキル基であり、Ｒ55は炭素数１～２０のアルキル基、炭素数６～２０のアリール基、又は炭素数７～２０のアラルキル基であり、Ｒ56は各々独立に炭素数１～５のアルキレン基である。ｋは１～５の整数であり、ｌは０～１３の整数であり、ｍは各々独立に０～５の整数である。
　これらの中でも、レジストのパターニング特性の観点からは、Ｒ51～Ｒ54は水素原子が好ましく、ｋは２が好ましく、ｌ及びｍは０が好ましい。 In the above general formula (a5), R 51 to R 54 are independently composed of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 56 is an alkylene group having 1 to 5 carbon atoms independently. be. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5 independently.
Among these, from the viewpoint of the patterning characteristics of the resist, hydrogen atoms are preferable for R 51 to R 54 , 2 is preferable for k, and 0 is preferable for l and m.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
上記一般式（ａ６）において、ｎ及びｏはそれぞれ独立に１～９の整数である。Ｒ23は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ23は互いに同一であっても異なっていてもよい。 In the above general formula (a6), n and o are independently integers of 1 to 9. R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 23s existing in one molecule may be the same or different from each other.
　これらの中で、レジストパターニング特性の観点から一般式（ａ１）～（ａ６）のいずれかで表されるエポキシ化合物を用いるのが好ましく、（ａ３）、（ａ４）、又は（ａ５）で表されるエポキシ化合物がより好ましく、（ａ５）で表されるエポキシ化合物がさらに好ましい。 Among these, from the viewpoint of resist patterning characteristics, it is preferable to use the epoxy compound represented by any of the general formulas (a1) to (a6), and it is represented by (a3), (a4) or (a5). The epoxy compound is more preferable, and the epoxy compound represented by (a5) is further preferable.
　不飽和一塩基酸（ｂ）は、１分子中に１個のみの酸基と１個以上のラジカル重合性不飽和結合を有する化合物であればよく、酸基としてはカルボキシ基であることが好ましい。
　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させることにより、酸基がエポキシ化合物のエポキシ基と反応して、エポキシ化合物中にラジカル重合性二重結合を導入した中間体を得ることができる。 The unsaturated monobasic acid (b) may be any compound having only one acid group in one molecule and one or more radically polymerizable unsaturated bonds, and the acid group is preferably a carboxy group. ..
By reacting the epoxy compound (a) with the unsaturated monobasic acid (b), the acid group reacts with the epoxy group of the epoxy compound to form an intermediate in which a radically polymerizable double bond is introduced into the epoxy compound. Obtainable.
　不飽和一塩基酸（ｂ）としては、例えば、（メタ）アクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸、（メタ）アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体などのモノカルボン酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルアジピン酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルマレイン酸、２－（メタ）アクリロイロキシプロピルコハク酸、２－（メタ）アクリロイロキシプロピルアジピン酸、２－（メタ）アクリロイロキシプロピルテトラヒドロフタル酸、２－（メタ）アクリロイロキシプロピルフタル酸、２－（メタ）アクリロイロキシプロピルマレイン酸、２－（メタ）アクリロイロキシブチルコハク酸、２－（メタ）アクリロイロキシブチルアジピン酸、２－（メタ）アクリロイロキシブチルヒドロフタル酸、２－（メタ）アクリロイロキシブチルフタル酸、２－（メタ）アクリロイロキシブチルマレイン酸、（メタ）アクリル酸にε－カプロラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン等のラクトン類を付加させ末端に１個のカルボキシ基を有する単量体、ヒドロキシアルキル（メタ）アクリレートのような末端に１個の水酸基を有する単量体、ペンタエリスリトールトリ（メタ）アクリレートのような末端に１個の水酸基を有する化合物に、（無水）コハク酸、（無水）フタル酸、（無水）マレイン酸などの酸（無水物）を付加させ、１個以上のエチレン不飽和基と末端に１個のカルボキシ基を有する（メタ）アクリル酸エステル、（メタ）アクリル酸ダイマーが挙げられる。 Examples of the unsaturated monobasic acid (b) include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, and nitro. Monocarboxylic acids such as cyano substituents, 2- (meth) acrylicyloxyethyl succinic acid, 2- (meth) acrylicyloxyethyl adipic acid, 2- (meth) acrylicyloxyethyl phthalic acid, 2- (meth) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) Acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutylsuccinic acid, 2- (meth) acrylic Ε to leuroxybutyladipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid, (meth) acrylic acid -A monomer having one carboxy group at the end by adding lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, and one at the end such as hydroxyalkyl (meth) acrylate. A monomer having a hydroxyl group, a compound having one hydroxyl group at the terminal such as pentaerythritol tri (meth) acrylate, and an acid such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid ( Examples thereof include (meth) acrylic acid ester and (meth) acrylic acid dimer having one or more ethylene unsaturated groups and one carboxy group at the terminal by adding (anhydrous).
　レジスト感度と経時安定性の観点から、不飽和一塩基酸（ｂ）としては、アルケニルカルボン酸が好ましく、（メタ）アクリル酸がより好ましい。 From the viewpoint of resist sensitivity and stability over time, the unsaturated monobasic acid (b) is preferably an alkenylcarboxylic acid, and more preferably a (meth) acrylic acid.
　中間体を得るための反応に用いられる溶媒としては、有機溶媒が挙げられ、例えば、プロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテート、３-メトキシプロピオン酸メチル、エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブ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、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、トルエン、キシレンを用いることができる。これらの中でも、反応収率の観点からプロピレングリコールモノメチルエーテルアセテート、３－メトキシブチルアセテートが好ましく、プロピレングリコールモノメチルエーテルアセテートがより好ましい。 Examples of the solvent used in the reaction for obtaining the intermediate include organic solvents, for example, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methyl 3-methoxypropionate, ethylene glycol monomethyl ether acetate, and ethylene glycol mono. Ethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene and xylene can be used. Among these, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate are preferable, and propylene glycol monomethyl ether acetate is more preferable, from the viewpoint of reaction yield.
　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）を反応させ、中間体を得る方法としては、公知の手法を用いることができる。例えば、溶媒中、触媒及び重合禁止剤の存在下、５０～１５０℃の温度で、エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させることができる。 A known method can be used as a method for obtaining an intermediate by reacting the epoxy compound (a) with the unsaturated monobasic acid (b). For example, the epoxy compound (a) and the unsaturated monobasic acid (b) can be reacted at a temperature of 50 to 150 ° C. in a solvent in the presence of a catalyst and a polymerization inhibitor.
　触媒としては、例えば、トリエチルホスフィン、トリブチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン等の３級ホスフィン、トリエチルアミン、トリメチルアミン、ベンジルジメチルアミン、ベンジルジエチルアミン等の３級アミン、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド等の４級アンモニウム塩を用いることができる。これらの中でも、反応収率の観点から、３級ホスフィンが好ましく、トリフェニルホスフィンがより好ましい。 Examples of the catalyst include tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. A quaternary ammonium salt such as dodecyltrimethylammonium chloride can be used. Among these, tertiary phosphine is preferable, and triphenylphosphine is more preferable, from the viewpoint of reaction yield.
　重合禁止剤としては、例えば、ヒドロキノン、メチルヒドロキノン、トリメチルヒドロキノン、パラメトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾールを用いることができる。これらの中でも、反応収率及びレジスト感度の観点からパラメトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾールが好ましく、パラメトキシフェノールがより好ましい。 As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, trimethylhydroquinone, paramethoxyphenol, and 2,6-di-tert-butyl-4-cresol can be used. Among these, paramethoxyphenol and 2,6-di-tert-butyl-4-cresol are preferable, and paramethoxyphenol is more preferable, from the viewpoint of reaction yield and resist sensitivity.
　なお、エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）、中間体を得るための反応に用いられる溶媒、触媒及び重合禁止剤は、いずれも１種を単独で用いてもよく、２種以上を併用してもよい。 The epoxy compound (a), the unsaturated monobasic acid (b), the solvent used in the reaction for obtaining the intermediate, the catalyst, and the polymerization inhibitor may be used alone or in combination of two. The above may be used together.
　不飽和一塩基酸（ｂ）の使用量は、エポキシ化合物（ａ）のエポキシ基１当量に対し０．５～１．５当量の範囲が好ましく、さらに好ましくは０．８～１．２当量の範囲である。不飽和一塩基酸（ｂ）の使用量を前記下限値以上とすることで残存エポキシ量が減少し、工程Ａにおける多塩基酸無水物との反応時のゲル化を抑制できる傾向がある。また、使用量を前記上限値以下とすることで不飽和一塩基酸（ｂ）が未反応物として残存するのを抑制できる傾向がある。 The amount of the unsaturated monobasic acid (b) used is preferably in the range of 0.5 to 1.5 equivalents with respect to 1 equivalent of the epoxy group of the epoxy compound (a), and more preferably 0.8 to 1.2 equivalents. It is a range. By setting the amount of the unsaturated monobasic acid (b) to be equal to or higher than the lower limit, the amount of residual epoxy tends to decrease, and gelation during the reaction with the polybasic acid anhydride in step A tends to be suppressed. Further, by setting the amount to be used to the upper limit or less, there is a tendency that the unsaturated monobasic acid (b) can be suppressed from remaining as an unreacted product.
　多塩基酸二無水物（ｃ）としては、１分子中に２個のみの酸無水物基を有する化合物であればよい。レジストのパターニング特性の観点から一般式（ｃ１）で表される化合物を含むことが好ましい。 The polybasic acid dianhydride (c) may be a compound having only two acid anhydride groups in one molecule. From the viewpoint of the patterning characteristics of the resist, it is preferable to contain the compound represented by the general formula (c1).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上記式（ｃ１）中、Ａは多塩基酸二無水物に由来する４価の有機基である。 In the above formula (c1), A is a tetravalent organic group derived from polybasic acid dianhydride.
　一般式（ｃ１）で表される多塩基酸二無水物（ｃ）としては、例えば、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、ビシクロヘキシルテトラカルボン酸二無水物、ピロメリット酸無水物、ベンゾフェノンテトラカルボン酸二無水物を用いることができる。これらの中でも、レジストのパターニング特性の観点から、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、ピロメリット酸無水物が好ましく、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）がより好ましい。 Examples of the polybasic acid dianhydride (c) represented by the general formula (c1) include biphenyltetracarboxylic acid dianhydride (BPDA), bicyclohexyltetracarboxylic acid dianhydride, pyromellitic acid anhydride, and benzophenone. Tetracarboxylic acid dianhydride can be used. Among these, biphenyltetracarboxylic acid dianhydride (BPDA) and pyromellitic acid anhydride are preferable, and biphenyltetracarboxylic acid dianhydride (BPDA) is more preferable from the viewpoint of the patterning property of the resist.
　多塩基酸一無水物（ｄ）としては、１分子中に１個のみの酸無水物基を有する化合物であればよい。例えば、マレイン酸無水物、コハク酸無水物、イタコン酸無水物、フタル酸無水物、テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、メチルテトラヒドロフタル酸無水物、メチルナジック酸無水物、ナジック酸無水物、トリメリット酸無水物を用いることができる。これらの中でも、レジストのパターニング特性の観点から、コハク酸無水物、フタル酸無水物、テトラヒドロフタル酸無水物が好ましく、テトラヒドロフタル酸無水物がより好ましい。 The polybasic acid anhydride (d) may be a compound having only one acid anhydride group in one molecule. For example, maleic acid anhydride, succinic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, methyltetrahydrophthalic acid anhydride, methylnagic acid anhydride, nagic acid. Anhydride and trimellitic acid anhydride can be used. Among these, succinic acid anhydride, phthalic acid anhydride, and tetrahydrophthalic acid anhydride are preferable, and tetrahydrophthalic acid anhydride is more preferable, from the viewpoint of the patterning property of the resist.
　多塩基酸二無水物（ｃ）及び多塩基酸一無水物（ｄ）はいずれも１種を単独で用いてもよく、２種以上を併用してもよい。 As the polybasic acid dianhydride (c) and the polybasic acid monoanhydride (d), one type may be used alone, or two or more types may be used in combination.
　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られた中間体と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させ、第一のカルボキシ基含有樹脂含有液を得る反応に関しても、公知の手法を用いることができる。例えば、中間体を含む中間体溶液に、多塩基酸二無水物（ｃ）及び多塩基酸一無水物（ｄ）を追加で投入し、５０～１５０℃の温度で反応させることができる。 An intermediate obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d) are used as an organic solvent. A known method can also be used for the reaction in which the reaction is carried out to obtain the first carboxy group-containing resin-containing liquid. For example, the polybasic acid dianhydride (c) and the polybasic acid monoanhydride (d) can be additionally added to the intermediate solution containing the intermediate and reacted at a temperature of 50 to 150 ° C.
　中間体と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを反応させる際に、さらに多価アルコール（ｅ）を加えて反応させてもよい。多価アルコール（ｅ）を加えて反応させることにより、カルボキシ基含有樹脂に多分岐構造を導入することで、経時安定性やレジストパターニング特性が向上する。 When the intermediate, the polybasic acid dianhydride (c), and the polybasic acid monoanhydride (d) are reacted, a polyhydric alcohol (e) may be further added and reacted. By introducing a multi-branched structure into the carboxy group-containing resin by adding the polyhydric alcohol (e) and reacting it, the stability over time and the resist patterning characteristics are improved.
　多価アルコール（ｅ）としては、例えば、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトールを用いることができる。これらの中でも、レジスト感度と経時安定性の観点から、トリメチロールプロパンが好ましい。 As the polyhydric alcohol (e), for example, trimethylolpropane, pentaerythritol, and dipentaerythritol can be used. Among these, trimethylolpropane is preferable from the viewpoint of resist sensitivity and stability over time.
　多価アルコール（ｅ）の使用量は、不飽和一塩基酸（ｂ）１当量に対し、０．０１当量以上が好ましく、０．０２当量以上がより好ましい。また、１当量以下が好ましく、０．７当量以下がより好ましく、０．５当量以下がさらに好ましく、０．３当量以下が特に好ましい。前記下限値以上とすることで、経時安定性が向上する傾向があり、また、前記上限値以下とすることでレジスト感度向上する傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～１当量が好ましく、０．０１～０．７当量がより好ましく、０．０２～０．５当量がさらに好ましく、０．０２～０．３当量が特に好ましい。 The amount of the polyhydric alcohol (e) used is preferably 0.01 equivalent or more, more preferably 0.02 equivalent or more, relative to 1 equivalent of the unsaturated monobasic acid (b). Further, 1 equivalent or less is preferable, 0.7 equivalent or less is more preferable, 0.5 equivalent or less is further preferable, and 0.3 equivalent or less is particularly preferable. When it is at least the lower limit value, the stability with time tends to be improved, and when it is at least the upper limit value, the resist sensitivity tends to be improved.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1 equivalent is preferable, 0.01 to 0.7 equivalent is more preferable, 0.02 to 0.5 equivalent is further preferable, and 0.02 to 0.3 equivalent is particularly preferable.
　多塩基酸二無水物（ｃ）の使用量は、多塩基酸一無水物（ｄ）１当量に対し、０．１当量以上が好ましく、０．３当量以上がより好ましく、０．５当量以上がさらに好ましい。また、５０当量以下が好ましく、４０当量以下がより好ましく、３０当量以下がさらに好ましい。前記下限値以上とすることで、レジストの密着性が向上する傾向があり、また、前記上限値以下とすることでレジストの残渣が低減する傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～５０当量が好ましく、０．３～４０当量がより好ましく、０．５～３０当量がさらに好ましい。 The amount of the polybasic acid dianhydride (c) to be used is preferably 0.1 equivalent or more, more preferably 0.3 equivalent or more, and 0.5 equivalent or more with respect to 1 equivalent of the polybasic acid monoanhydride (d). Is even more preferable. Further, 50 equivalents or less is preferable, 40 equivalents or less is more preferable, and 30 equivalents or less is further preferable. When the value is not less than the lower limit, the adhesion of the resist tends to be improved, and when the value is not more than the upper limit, the residue of the resist tends to be reduced.
The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 50 equivalents are preferred, 0.3 to 40 equivalents are more preferred, and 0.5 to 30 equivalents are even more preferred.
＜工程Ｂ＞
　工程Ｂにおいては、工程Ａで得られた第一のカルボキシ基含有樹脂含有液に水を添加して、第二のカルボキシ基含有樹脂含有液を得る。工程Ｂを有することで、得られるカルボキシ基含有樹脂含有液中のカルボキシ基含有樹脂の分子量や粘度の保管中における変化を抑制し、カルボキシ基含有樹脂を安定化することが可能となる。
　水は単独で添加してもよいし、中間体を得るための反応に用いられる溶媒として挙げた有機溶媒と水との混合物として添加してもよい。また、添加時のカルボキシ基含有樹脂含有液の温度は、２０℃～８０℃が好ましく、３０℃～７０℃がより好ましく、４０℃～６０℃がさらに好ましく、４５℃～５５℃が特に好ましい。前記温度範囲とすることで、水をカルボキシ基含有樹脂含有液に均一に分散、溶解させることができる。
　水の添加はカルボキシ基含有樹脂含有液を攪拌しながら実施することが好ましい。これにより、水をカルボキシ基含有樹脂含有液に均一に分散、溶解させることができる。
　添加する水の量としては、第二のカルボキシ基含有樹脂含有液の含有水分率が０．１質量％以上が好ましく、０．１２質量％以上がより好ましく、０．１４質量％以上がさらに好ましく、０．１６質量％以上がことさら好ましく、０．１８質量％以上が特に好ましい。また、１質量％以下が好ましく、０．８質量％以下がより好ましく、０．６質量％以下がさらに好ましく、０．５質量％以下がことさら好ましく、０．４質量％以下が特に好ましい。前記下限値以上とすることで、経時安定性が向上する傾向がある。また、前記上限値以下とすることでレジストの密着性が向上する傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～１質量％が好ましく、０．１２～０．８質量％がより好ましく、０．１４～０．６質量％がさらに好ましく、０．１６～０．５質量％がことさら好ましく、０．１８～０．４質量％が特に好ましい。
　カルボキシ基含有樹脂含有液の含有水分率はＪＩＳ　Ｋ０１１３（２００５）記載のカールフィッシャー測定法で算出することができる。各種の水分計を用いることができるが、例えば、京都電子工業社製、ＭＫＡ－６１０などが挙げられる。 <Process B>
In step B, water is added to the first carboxy group-containing resin-containing liquid obtained in step A to obtain a second carboxy group-containing resin-containing liquid. By having the step B, it is possible to suppress changes in the molecular weight and viscosity of the carboxy group-containing resin in the obtained carboxy group-containing resin-containing liquid during storage, and to stabilize the carboxy group-containing resin.
Water may be added alone or as a mixture of water and the organic solvent mentioned as the solvent used in the reaction for obtaining an intermediate. The temperature of the carboxy group-containing resin-containing liquid at the time of addition is preferably 20 ° C to 80 ° C, more preferably 30 ° C to 70 ° C, further preferably 40 ° C to 60 ° C, and particularly preferably 45 ° C to 55 ° C. Within the temperature range, water can be uniformly dispersed and dissolved in the carboxy group-containing resin-containing liquid.
It is preferable to add water while stirring the carboxy group-containing resin-containing liquid. As a result, water can be uniformly dispersed and dissolved in the carboxy group-containing resin-containing liquid.
As for the amount of water to be added, the water content of the second carboxy group-containing resin-containing liquid is preferably 0.1% by mass or more, more preferably 0.12% by mass or more, still more preferably 0.14% by mass or more. , 0.16% by mass or more is particularly preferable, and 0.18% by mass or more is particularly preferable. Further, 1% by mass or less is preferable, 0.8% by mass or less is more preferable, 0.6% by mass or less is further preferable, 0.5% by mass or less is particularly preferable, and 0.4% by mass or less is particularly preferable. By setting the value to the lower limit or higher, the stability over time tends to be improved. Further, when the value is not more than the upper limit, the adhesion of the resist tends to be improved.
The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 1% by mass is preferable, 0.12 to 0.8% by mass is more preferable, 0.14 to 0.6% by mass is further preferable, and 0.16 to 0.5% by mass is particularly preferable. , 0.18 to 0.4% by mass is particularly preferable.
The water content of the carboxy group-containing resin-containing liquid can be calculated by the Karl Fischer titer measurement method described in JIS K0113 (2005). Various moisture meters can be used, and examples thereof include MKA-610 manufactured by Kyoto Denshi Kogyo Co., Ltd.
　本発明の方法で製造されるカルボキシ基含有樹脂の酸価は、１０ｍｇＫＯＨ／ｇ以上が好ましく、３０ｍｇＫＯＨ／ｇ以上がより好ましく、５０ｍｇＫＯＨ／ｇ以上がさらに好ましく、８０ｍｇＫＯＨ／ｇ以上が特に好ましい。また、２５０ｍｇＫＯＨ／ｇ以下が好ましく、２００ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１３０ｍｇＫＯＨ／ｇ以下が特に好ましい。前記下限値以上とすることで、レジストの残渣が低減する傾向がある。また、前記上限値以下とすることでレジストの密着性が向上する傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～２５０ｍｇＫＯＨ／ｇが好ましく、３０～２００ｍｇＫＯＨ／ｇがより好ましく、５０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、８０～１３０ｍｇＫＯＨ／ｇが特に好ましい。 The acid value of the carboxy group-containing resin produced by the method of the present invention is preferably 10 mgKOH / g or more, more preferably 30 mgKOH / g or more, further preferably 50 mgKOH / g or more, and particularly preferably 80 mgKOH / g or more. Further, 250 mgKOH / g or less is preferable, 200 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, and 130 mgKOH / g or less is particularly preferable. By setting the value to the lower limit or more, the residue of the resist tends to be reduced. Further, when the value is not more than the upper limit, the adhesion of the resist tends to be improved.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 250 mgKOH / g is preferable, 30 to 200 mgKOH / g is more preferable, 50 to 150 mgKOH / g is further preferable, and 80 to 130 mgKOH / g is particularly preferable.
　本発明の製造方法で製造されるカルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂（「本発明の製造方法で製造されるカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂」とも言う。）の重量平均分子量は、３０００以上が好ましく、５０００以上がより好ましく、８０００以上がさらに好ましく、１２０００以上が特に好ましい。また、２２０００以下が好ましく、２１０００以下がより好ましい。前記下限値以上とすることで、レジストの密着性が向上する傾向がある。また、前記上限値以下とすることでレジストの残渣が低減する傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、３０００～２２０００が好ましく、５０００～２２０００がより好ましく、８０００～２１０００がさらに好ましく、１２０００～２１０００が特に好ましい。 The carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid produced by the production method of the present invention is also referred to as "carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid produced by the production method of the present invention". ), The weight average molecular weight is preferably 3000 or more, more preferably 5000 or more, further preferably 8000 or more, and particularly preferably 12000 or more. Further, 22000 or less is preferable, and 21000 or less is more preferable. By setting the value to the lower limit or more, the adhesion of the resist tends to be improved. Further, when the value is not more than the upper limit, the residue of the resist tends to be reduced.
The above upper and lower limits can be combined arbitrarily. For example, 3000 to 22000 is preferable, 5000 to 22000 is more preferable, 8000 to 21000 is further preferable, and 12000 to 21000 is particularly preferable.
［カルボキシ基含有樹脂含有液］
　本発明のカルボキシ基含有樹脂含有液は、カルボキシ基含有樹脂、有機溶媒及び水を含有し、含有水分率が０．１質量％以上１質量％以下である。
　含有水分率が前記範囲内であることにより、カルボキシ基含有樹脂含有液中のカルボキシ基含有樹脂の分子量や粘度の保管中における変化を抑制し、カルボキシ基含有樹脂を安定化することが可能となる。また、カルボキシ基含有樹脂含有液を用いたレジストの密着性が向上する傾向がある。
　カルボキシ基含有樹脂含有液の含有水分率は、０．１質量％以上１質量％以下であり、０．１２質量％以上がより好ましく、０．１４質量％以上がさらに好ましく、０．１６質量％以上がことさら好ましく、０．１８質量％以上が特に好ましい。また、０．８質量％以下がより好ましく、０．６質量％以下がさらに好ましく、０．５質量％以下がことさら好ましく、０．４質量％以下が特に好ましい。上記の上限及び下限は任意に組み合わせることができ、例えば、０．１２質量％以上０．８質量％以下が好ましく、０．１４質量％以上０．６質量％以下がより好ましく、０．１６質量％以上０．５質量％以下がさらに好ましく、０．１８質量％以上０．４質量％以下が特に好ましい。前記下限値以上とすることで、経時安定性が向上する傾向がある。また、前記上限値以下とすることでレジストの密着性が向上する傾向がある。 [Carboxy group-containing resin-containing liquid]
The carboxy group-containing resin-containing liquid of the present invention contains a carboxy group-containing resin, an organic solvent and water, and has a water content of 0.1% by mass or more and 1% by mass or less.
When the water content is within the above range, changes in the molecular weight and viscosity of the carboxy group-containing resin in the carboxy group-containing resin-containing liquid during storage can be suppressed, and the carboxy group-containing resin can be stabilized. .. Further, the adhesion of the resist using the carboxy group-containing resin-containing liquid tends to be improved.
The water content of the carboxy group-containing resin-containing liquid is 0.1% by mass or more and 1% by mass or less, more preferably 0.12% by mass or more, further preferably 0.14% by mass or more, and 0.16% by mass. The above is particularly preferable, and 0.18% by mass or more is particularly preferable. Further, 0.8% by mass or less is more preferable, 0.6% by mass or less is further preferable, 0.5% by mass or less is particularly preferable, and 0.4% by mass or less is particularly preferable. The above upper limit and lower limit can be arbitrarily combined, and for example, 0.12% by mass or more and 0.8% by mass or less are preferable, 0.14% by mass or more and 0.6% by mass or less is more preferable, and 0.16% by mass is preferable. % Or more and 0.5% by mass or less are more preferable, and 0.18% by mass or more and 0.4% by mass or less are particularly preferable. By setting the value to the lower limit or higher, the stability over time tends to be improved. Further, when the value is not more than the upper limit value, the adhesion of the resist tends to be improved.
　本発明のカルボキシ基含有樹脂含有液は、本発明の製造方法で製造されたカルボキシ基含有樹脂含有液であることが好ましい。
　本発明のカルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂は、エポキシ化合物（ａ）由来の構造を有することが好ましい。
　本発明のカルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂は、不飽和一塩基酸（ｂ）由来の構造を有することが好ましい。
　本発明のカルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂は、多塩基酸二無水物（ｃ）由来の構造を有することが好ましい。
　本発明のカルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂は、多塩基酸一無水物（ｄ）に由来する構造を有することが好ましい。
　本発明のカルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂は、多価アルコール（ｅ）に由来する構造を有することが好ましい。
　エポキシ化合物（ａ）、不飽和一塩基酸（ｂ）、多塩基酸二無水物（ｃ）、多塩基酸一無水物（ｄ）、多価アルコール（ｅ）の好ましい種類や好ましい配合量等は、カルボキシ基含有樹脂含有液の製造方法で前述した種類や配合量等と同様である。 The carboxy group-containing resin-containing liquid of the present invention is preferably a carboxy group-containing resin-containing liquid produced by the production method of the present invention.
The carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the epoxy compound (a).
The carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the unsaturated monobasic acid (b).
The carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the polybasic acid dianhydride (c).
The carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the polybasic acid monoanhydride (d).
The carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid of the present invention preferably has a structure derived from the polyhydric alcohol (e).
Preferred types and amounts of the epoxy compound (a), unsaturated monobasic acid (b), polybasic acid dianhydride (c), polybasic acid monoanhydride (d), polyhydric alcohol (e), etc. , The method for producing a carboxy group-containing resin-containing liquid is the same as the above-mentioned type and blending amount.
　本発明のカルボキシ基含有樹脂含有液に含有される有機溶媒としては、本発明のカルボキシ基含有樹脂含有液の製造方法で用いられる有機溶媒を好ましく用いることができる。 As the organic solvent contained in the carboxy group-containing resin-containing liquid of the present invention, the organic solvent used in the method for producing the carboxy group-containing resin-containing liquid of the present invention can be preferably used.
［感光性樹脂組成物］
　本発明の感光性樹脂組成物の製造方法は、（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤を含む感光性樹脂組成物の製造方法であり、（Ａ）アルカリ可溶性樹脂として、本発明の製造方法で製造されるカルボキシ基含有樹脂含有液を配合することを含む。
　また、本発明の感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー、（Ｃ）光重合開始剤を含有し、（Ａ）アルカリ可溶性樹脂として、本発明のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含む。
　以下、本発明の感光性樹脂組成物の製造方法で製造される感光性樹脂組成物及び本発明の感光性樹脂組成物を合わせて「本発明における感光性樹脂組成物」と称する。 [Photosensitive resin composition]
The method for producing a photosensitive resin composition of the present invention is a method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator. ) The alkali-soluble resin includes a carboxy group-containing resin-containing liquid produced by the production method of the present invention.
Further, the photosensitive resin composition of the present invention contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator, and is a carboxy of the present invention as (A) an alkali-soluble resin. Contains a carboxy group-containing resin derived from a group-containing resin-containing liquid.
Hereinafter, the photosensitive resin composition produced by the method for producing a photosensitive resin composition of the present invention and the photosensitive resin composition of the present invention are collectively referred to as "photosensitive resin composition in the present invention".
＜（Ａ）アルカリ可溶性樹脂＞
　本発明における感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂として、本発明のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂、すなわち本発明の製造方法で製造されるカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含むことにより、カルボキシ基含有樹脂含有液中のカルボキシ基含有樹脂の分子量や粘度の保管中における変化を抑制し、カルボキシ基含有樹脂を安定化することが可能となる。
　（Ａ）アルカリ可溶性樹脂は、その他のアルカリ可溶性樹脂を含有してもよい。 <(A) Alkali-soluble resin>
The photosensitive resin composition in the present invention contains, as (A) an alkali-soluble resin, a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid of the present invention, that is, a carboxy group-containing resin produced by the production method of the present invention. By containing the carboxy group-containing resin derived from the liquid, it is possible to suppress changes in the molecular weight and viscosity of the carboxy group-containing resin in the carboxy group-containing resin-containing liquid during storage and stabilize the carboxy group-containing resin. Become.
(A) The alkali-soluble resin may contain other alkali-soluble resins.
　その他のアルカリ可溶性樹脂としては、感光性樹脂組成物を塗布、乾燥して得られる塗膜を露光後、露光部と非露光部のアルカリ現像に対する溶解性が変化するようなものであれば、特に限定されないが、カルボキシ基を有するアルカリ可溶性樹脂であるのが好ましい。また、エチレン性不飽和基を有するものが好ましく、エチレン性不飽和基とカルボキシ基を有するアルカリ可溶性樹脂が、さらに好ましい。具体的には、カルボキシ基を有するエポキシ（メタ）アクリレート樹脂やアクリル共重合樹脂が挙げられ、具体的には、後述の（Ａ１－１）、（Ａ２－１）、（Ａ２－２）、（Ａ２－３）及び（Ａ２－４）として記載のアルカリ可溶樹脂が挙げられる。これらは１種を用いても２種以上を用いてもよい。上記の中でも、カルボキシ基を有するエポキシ（メタ）アクリレート樹脂（Ａ１－１）が特に好ましい。 Other alkali-soluble resins include those in which the solubility of the exposed portion and the non-exposed portion in alkaline development changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed. Although not limited, it is preferably an alkali-soluble resin having a carboxy group. Further, those having an ethylenically unsaturated group are preferable, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxy group is more preferable. Specific examples thereof include epoxy (meth) acrylate resins and acrylic copolymer resins having a carboxy group, and specific examples thereof include (A1-1), (A2-1), (A2-2), and (A1-2), which will be described later. Examples thereof include the alkali-soluble resins described as A2-3) and (A2-4). These may be used alone or in combination of two or more. Among the above, an epoxy (meth) acrylate resin (A1-1) having a carboxy group is particularly preferable.
　カラーフィルター作成時、アルカリ現像液に非露光部が溶解するために、高分子樹脂として、水酸基、カルボキシ基、リン酸基、スルホン酸基などの酸性の官能基を有した高分子樹脂が適用される。これらの中でもアルカリ現像液に対する溶解性の観点から、カルボキシ基を有した高分子樹脂が好ましい。また、リン酸基やスルホン酸基は、カルボキシ基よりも酸性度は高いものの、感光性樹脂組成物中の塩基性基を有する開始剤、モノマー、分散剤、その他の添加剤などと反応しやすく、保存安定性が悪くなる場合がある。 When creating a color filter, a polymer resin having an acidic functional group such as a hydroxyl group, a carboxy group, a phosphoric acid group, or a sulfonic acid group is applied as the polymer resin in order to dissolve the non-exposed portion in the alkaline developing solution. To. Among these, a polymer resin having a carboxy group is preferable from the viewpoint of solubility in an alkaline developer. Further, although the phosphate group and the sulfonic acid group have higher acidity than the carboxy group, they easily react with the initiator, the monomer, the dispersant, and other additives having a basic group in the photosensitive resin composition. , Storage stability may deteriorate.
　カルボキシ基を有するエポキシ（メタ）アクリレート樹脂としては、例えば、以下のエポキシ（メタ）アクリレート樹脂（Ａ１－１）が挙げられる。 Examples of the epoxy (meth) acrylate resin having a carboxy group include the following epoxy (meth) acrylate resin (A1-1).
＜エポキシ（メタ）アクリレート樹脂（Ａ１－１）＞
　エポキシ化合物に不飽和一塩基酸を付加させ、さらに、多塩基酸一無水物を反応させることによって得られたアルカリ可溶性樹脂。 <Epoxy (meth) acrylate resin (A1-1)>
An alkali-soluble resin obtained by adding an unsaturated monobasic acid to an epoxy compound and further reacting it with a polybasic acid monoanhydride.
＜カルボキシ基とエチレン性不飽和基結合を有するエポキシ（メタ）アクリレート樹脂（Ａ１－１）＞
　原料となるエポキシ化合物として、例えば、ビスフェノールＡ型エポキシ樹脂（例えば、三菱ケミカル社製の「ｊＥＲ（登録商標。以下同じ。）８２８」、「ｊＥＲ１００１」、「ｊＥＲ１００２」、「ｊＥＲ１００４」等）、ビスフェノールＡ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ（例えば、日本化薬社製の「ＮＥＲ－１３０２」（エポキシ当量３２３，軟化点７６℃））、ビスフェノールＦ型樹脂（例えば、三菱ケミカル社製の「ｊＥＲ８０７」、「ＥＰ－４００１」、「ＥＰ－４００２」、「ＥＰ－４００４等」）、ビスフェノールＦ型エポキシ樹脂のアルコール性水酸基とエピクロルヒドリンの反応により得られるエポキシ樹脂（例えば、日本化薬社製の「ＮＥＲ－７４０６」（エポキシ当量３５０，軟化点６６℃））、ビスフェノールＳ型エポキシ樹脂、ビフェニルグリシジルエーテル（例えば、三菱ケミカル社製の「ＹＸ－４０００」）、フェノールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ－２０１」、三菱ケミカル社製の「ＥＰ－１５２」、「ＥＰ－１５４」、ダウケミカル社製の「ＤＥＮ－４３８」）、（ｏ，ｍ，ｐ－）クレゾールノボラック型エポキシ樹脂（例えば、日本化薬社製の「ＥＯＣＮ（登録商標。以下同じ。）－１０２Ｓ」、「ＥＯＣＮ－１０２０」、「ＥＯＣＮ－１０４Ｓ」）、トリグリシジルイソシアヌレート（例えば、日産化学社製の「ＴＥＰＩＣ（登録商標）」）、トリスフェノールメタン型エポキシ樹脂（例えば、日本化薬社製の「ＥＰＰＮ（登録商標。以下同じ。）－５０１」、「ＥＰＰＮ－５０２」、「ＥＰＰＮ－５０３」）、脂環式エポキシ樹脂（ダイセル社製の「セロキサイド（登録商標。以下同じ。）２０２１Ｐ」、「セロキサイドＥＨＰＥ」）、ジシクロペンタジエンとフェノールの反応によるフェノール樹脂をグリシジル化したエポキシ樹脂（例えば、ＤＩＣ社製の「ＥＸＡ－７２００」、日本化薬社製の「ＮＣ－７３００」）、下記一般式（ａ１）～（ａ６）で表されるエポキシ樹脂を好適に用いることができる。
　具体的には、例えば、下記一般式（ａ１）で表されるエポキシ樹脂として日本化薬社製の「ＸＤ－１０００」、下記一般式（ａ２）で表されるエポキシ樹脂として日本化薬社製の「ＮＣ－３０００」、下記一般式（ａ４）で表されるエポキシ樹脂として新日鐵住金化学社製の「ＥＳＦ－３００」が挙げられる。 <Epoxy (meth) acrylate resin (A1-1) having a carboxy group and an ethylenically unsaturated group bond>
Examples of the epoxy compound as a raw material include bisphenol A type epoxy resin (for example, "jER (registered trademark; the same applies hereinafter) 828", "jER1001", "jER1002", "jER1004", etc.) manufactured by Mitsubishi Chemical Corporation, bisphenol. Epoxy obtained by the reaction of the alcoholic hydroxyl group of the A-type epoxy resin with epichlorohydrin (for example, "NER-1302" (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, Mitsubishi). "JER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Chemical Corporation), an epoxy resin obtained by the reaction of an alcoholic hydroxyl group of a bisphenol F type epoxy resin with epichlorohydrin (for example, Japan). "NER-7406" manufactured by Kayakusha (epoxy equivalent 350, softening point 66 ° C), bisphenol S type epoxy resin, biphenyl glycidyl ether (for example, "YX-4000" manufactured by Mitsubishi Chemical Corporation), phenol novolac type epoxy Resins (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Corporation), (o, m, p-) Cresol novolak type epoxy resin (for example, "EOCN (registered trademark. The same shall apply hereinafter) -102S", "EOCN-1020", "EOCN-104S") manufactured by Nippon Kayaku Co., Ltd., triglycidyl isocyanurate (for example). , Nissan Chemical Corporation "TEPIC (registered trademark)"), Trisphenol methane type epoxy resin (for example, "EPPN (registered trademark. The same shall apply hereinafter) -501", "EPPN-502" manufactured by Nippon Kayaku Co., Ltd., "EPPN-503"), alicyclic epoxy resin ("Ceroxide (registered trademark; the same shall apply hereinafter) 2021P" manufactured by Daicel Co., Ltd., "Ceroxyside EHPE"), and a phenol resin obtained by the reaction of dicyclopentadiene with phenol was glycidylated. Epoxy resins (for example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.) and epoxy resins represented by the following general formulas (a1) to (a6) can be preferably used. can.
Specifically, for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a1), and Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a2). "NC-3000" and "ESF-300" manufactured by Nippon Steel & Sumitomo Metal Corporation can be mentioned as an epoxy resin represented by the following general formula (a4).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記一般式（ａ１）において、ｂ１１は平均値を示し、０～１０の数を示す。Ｒ11は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ11は互いに同一であっても異なっていてもよい。 In the above general formula (a1), b11 indicates an average value and indicates a number from 0 to 10. R 11 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 11s existing in one molecule may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記一般式（ａ２）において、ｂ１２は平均値を示し、０～１０の数を示す。Ｒ21は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ21は互いに同一であっても異なっていてもよい。 In the above general formula (a2), b12 indicates an average value and indicates a number from 0 to 10. R 21 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 21s existing in one molecule may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記一般式（ａ３）において、Ｘは下記一般式（ａ３－１）又は（ａ３－２）で表される連結基を示す。但し、分子構造中に１つ以上のアダマンタン構造を含む。ｂ１３は２又は３の整数を示す。 In the above general formula (a3), X represents a linking group represented by the following general formula (a3-1) or (a3-2). However, the molecular structure contains one or more adamantane structures. b13 indicates an integer of 2 or 3.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記一般式（ａ３－１）及び（ａ３－２）において、Ｒ31～Ｒ34及びＲ35～Ｒ37は、各々独立に、置換基を有していてもよいアダマンチル基、水素原子、置換基を有していてもよい炭素数１～１２のアルキル基、又は置換基を有していてもよいフェニル基を示す。また、式中の＊は式（ａ３）中の結合部位を表す。
　式（ａ３－１）としては、レジストのパターニング特性の観点から、アダマンチル基と水素原子をそれぞれ２つずつ有することが好ましい。式（ａ３－２）としては、レジストのパターニング特性の観点から、アダマンチル基２つと水素原子を１つ有することが好ましい。 In the above general formulas (a3-1) and (a3-2), R 31 to R 34 and R 35 to R 37 each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. Indicates an alkyl group having 1 to 12 carbon atoms which may have an alkyl group, or a phenyl group which may have a substituent. Further, * in the formula represents a binding site in the formula (a3).
The formula (a3-1) preferably has two adamantyl groups and two hydrogen atoms, respectively, from the viewpoint of the patterning characteristics of the resist. The formula (a3-2) preferably has two adamantyl groups and one hydrogen atom from the viewpoint of the patterning characteristics of the resist.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　上記一般式（ａ４）において、ｐ及びｑは各々独立に０～４の整数を表し、Ｒ41及びＲ42は各々独立に炭素数１～２０のアルキル基又はハロゲン原子を表す。Ｒ43及びＲ44は各々独立に炭素数１～５のアルキレン基を表す。ｘ及びｙはそれぞれ独立して０以上の整数を表す。 In the above general formula (a4), p and q each independently represent an integer of 0 to 4, and R 41 and R 42 each independently represent an alkyl group or a halogen atom having 1 to 20 carbon atoms. R 43 and R 44 each independently represent an alkylene group having 1 to 5 carbon atoms. x and y each independently represent an integer of 0 or more.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記一般式（ａ５）において、Ｒ51～Ｒ54は各々独立に、水素原子、炭素数１～２０のアルキル基、炭素原子６～２０のアリール基、又は、炭素原子７～２０のアラルキル基であり、Ｒ55は炭素数１～２０のアルキル基、炭素数６～２０のアリール基、又は炭素数７～２０のアラルキル基であり、Ｒ56は各々独立に炭素数１～５のアルキレン基である。ｋは１～５の整数であり、ｌは０～１３の整数であり、ｍは各々独立に０～５の整数である。 In the above general formula (a5), R 51 to R 54 are independently composed of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R 55 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R 56 is an alkylene group having 1 to 5 carbon atoms independently. be. k is an integer of 1 to 5, l is an integer of 0 to 13, and m is an integer of 0 to 5 independently.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　上記一般式（ａ６）において、ｎ及びｏはそれぞれ独立に１～９の整数である。
　Ｒ23は水素原子、ハロゲン原子、炭素数１～８のアルキル基、炭素数３～１０のシクロアルキル基、フェニル基、ナフチル基、又はビフェニル基を表す。なお、１分子中に存在する複数のＲ23は互いに同一であっても異なっていてもよい。 In the above general formula (a6), n and o are independently integers of 1 to 9.
R 23 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. The plurality of R 23s existing in one molecule may be the same or different from each other.
　これらの中で、一般式（ａ１）、（ａ２）又は（ａ６）のいずれかで表されるエポキシ化合物を用いるのが好ましい。 Among these, it is preferable to use an epoxy compound represented by any of the general formulas (a1), (a2) or (a6).
　不飽和一塩基酸としては、例えば、（メタ）アクリル酸、クロトン酸、ｏ－、ｍ－、ｐ－ビニル安息香酸、（メタ）アクリル酸のα位ハロアルキル、アルコキシル、ハロゲン、ニトロ、シアノ置換体などのモノカルボン酸、２－（メタ）アクリロイロキシエチルコハク酸、２－（メタ）アクリロイロキシエチルアジピン酸、２－（メタ）アクリロイロキシエチルフタル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチルマレイン酸、２－（メタ）アクリロイロキシプロピルコハク酸、２－（メタ）アクリロイロキシプロピルアジピン酸、２－（メタ）アクリロイロキシプロピルテトラヒドロフタル酸、２－（メタ）アクリロイロキシプロピルフタル酸、２－（メタ）アクリロイロキシプロピルマレイン酸、２－（メタ）アクリロイロキシブチルコハク酸、２－（メタ）アクリロイロキシブチルアジピン酸、２－（メタ）アクリロイロキシブチルヒドロフタル酸、２－（メタ）アクリロイロキシブチルフタル酸、２－（メタ）アクリロイロキシブチルマレイン酸、
　（メタ）アクリル酸エステルとしては、（メタ）アクリル酸にε－カプロラクトン、β－プロピオラクトン、γ－ブチロラクトン、δ－バレロラクトン等のラクトン類を付加させ末端に１個の水酸基を有する単量体や、
　あるいはヒドロキシアルキル（メタ）アクリレートのような末端に１個の水酸基を有する単量体や、ペンタエリスリトールトリ（メタ）アクリレートのような末端に１個の水酸基を有する化合物に、（無水）コハク酸、（無水）フタル酸、（無水）マレイン酸などの酸（無水物）を付加させ、１個以上のエチレン不飽和基と末端に１個のカルボキシ基を有する（メタ）アクリル酸エステル、（メタ）アクリル酸ダイマーが挙げられる。 Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Monocarboxylic acids such as 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxy Ethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxy Propyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropyl maleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl Adipic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid,
The (meth) acrylic acid ester is a single amount having one hydroxyl group at the end by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone to (meth) acrylic acid. Body and
Alternatively, a monomer having one hydroxyl group at the terminal such as hydroxyalkyl (meth) acrylate, or a compound having one hydroxyl group at the terminal such as pentaerythritol tri (meth) acrylate, and (maleic) succinic acid, A (meth) acrylic acid ester having one or more ethylene unsaturated groups and one carboxy group at the end by adding an acid (anhydride) such as (anhydrous) phthalic acid or (maleic anhydride) maleic acid, (meth). Acrylic acid dimer can be mentioned.
　これらの内、感度の点から、特に好ましいものは（メタ）アクリル酸である。
　不飽和一塩基酸を付加させる方法としては、公知の手法を用いることができる。例えば、エステル化触媒の存在下、５０～１５０℃の温度で、不飽和一塩基酸とエポキシ化合物とを反応させることができる。ここで用いる触媒としては、トリエチルホスフィン、トリブチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン等の３級ホスフィン、トリエチルアミン、トリメチルアミン、ベンジルジメチルアミン、ベンジルジエチルアミン等の３級アミン、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、ドデシルトリメチルアンモニウムクロライド等の４級アンモニウム塩を用いることができる。 Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity.
As a method for adding an unsaturated monobasic acid, a known method can be used. For example, the unsaturated monobasic acid can be reacted with the epoxy compound at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. The catalyst used here includes tertiary phosphine such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amine such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride. , Quaternary ammonium salts such as dodecyltrimethylammonium chloride can be used.
　なお、エポキシ化合物、不飽和一塩基酸、及び触媒は、いずれも１種を単独で用いてもよく、２種以上を併用してもよい。
　不飽和一塩基酸の使用量は、エポキシ化合物のエポキシ基１当量に対し０．５～１．２当量の範囲が好ましく、さらに好ましくは０．７～１．１当量の範囲である。
　不飽和一塩基酸の使用量を前記下限値以上とすることで不飽和基の導入量が十分となり、引き続く多塩基酸一無水物との反応も十分となり、また、多量のエポキシ基の残存を抑制できる傾向がある。一方で、前記使用量を前記上限値以下とすることで不飽和一塩基酸が未反応物として残存するのを抑制できる傾向がある。 The epoxy compound, unsaturated monobasic acid, and catalyst may be used alone or in combination of two or more.
The amount of the unsaturated monobasic acid used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of the epoxy compound.
By setting the amount of unsaturated monobasic acid to be more than the above lower limit, the amount of unsaturated groups introduced becomes sufficient, the subsequent reaction with polybasic acid monoanhydride becomes sufficient, and a large amount of epoxy groups remain. It tends to be suppressed. On the other hand, by setting the amount to be used to be equal to or less than the upper limit, it tends to be possible to suppress the unsaturated monobasic acid from remaining as an unreacted product.
　多塩基酸一無水物としては、例えば、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、メチルヘキサヒドロフタル酸、エンドメチレンテトラヒドロフタル酸、クロレンド酸、メチルテトラヒドロフタル酸の一無水物から選ばれた、１種又は２種以上が挙げられる。 Examples of the polybasic acid monoanhydride include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, and chlorendic acid. , One or more selected from monoanhydrides of methyltetrahydrophthalic acid.
　好ましくは、マレイン酸、コハク酸、イタコン酸、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、ピロメリット酸、トリメリット酸の無水物である。特に好ましくは、テトラヒドロフタル酸、の一無水物である。 Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and trimellitic acid anhydrides. Particularly preferred is tetrahydrophthalic acid, a monoanhydride.
　多塩基酸一無水物の付加反応に関しても公知の手法を用いることができ、エポキシ化合物への不飽和一塩基酸の付加反応と同様な条件下で、継続反応させて目的物を得ることができる。多塩基酸一無水物成分の付加量は、生成するカルボキシ基含有エポキシ（メタ）アクリレート樹脂の酸価が１０～１５０ｍｇＫＯＨ／ｇの範囲となるような程度であることが好ましく、さらに２０～１４０ｍｇＫＯＨ／ｇの範囲となるような程度であることが好ましい。前記下限値以上とすることでアルカリ現像性が良好となる傾向がある。また、前記上限値以下とすることで硬化性が良好となる傾向がある。 A known method can also be used for the addition reaction of polybasic acid monoanhydride, and the desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of unsaturated monobasic acid to the epoxy compound. .. The amount of the polybasic acid monoanhydride component added is preferably such that the acid value of the produced carboxy group-containing epoxy (meth) acrylate resin is in the range of 10 to 150 mgKOH / g, and more preferably 20 to 140 mgKOH / g. It is preferably in the range of g. When the value is equal to or higher than the lower limit, the alkali developability tends to be good. Further, when the value is not more than the upper limit, the curability tends to be good.
　このようにして得られるエポキシ（メタ）アクリレート樹脂（Ａ１－１）の酸価は、通常１０ｍｇＫＯＨ／ｇ以上、好ましくは５０ｍｇＫＯＨ／ｇ以上、より好ましくは８０ｍｇＫＯＨ／ｇ以上であり、２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１５０ｍｇＫＯＨ／ｇ以下であることがより好ましい。前記下限値以上とすることで現像性が良好となる傾向がある。また、前記上限値以下とすることでアルカリ耐性を良好にすることができる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０～２００ｍｇＫＯＨ／ｇが好ましく、５０～２００ｍｇＫＯＨ／ｇがより好ましく、８０～１５０ｍｇＫＯＨ／ｇがさらに好ましい。 The acid value of the epoxy (meth) acrylate resin (A1-1) thus obtained is usually 10 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 80 mgKOH / g or more, and 200 mgKOH / g or less. It is preferably present, and more preferably 150 mgKOH / g or less. When the value is equal to or higher than the lower limit, the developability tends to be good. Further, the alkali resistance tends to be improved by setting the value to the upper limit or less.
The above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH / g is preferable, 50 to 200 mgKOH / g is more preferable, and 80 to 150 mgKOH / g is further preferable.
　エポキシ（メタ）アクリレート樹脂（Ａ１－１）のゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定によるポリスチレン換算の重量平均分子量（Ｍｗ）は、１０００以上が好ましく、１５００以上がより好ましく、２０００以上がさらに好ましく、２５００以上が特に好ましい。また、２００００以下が好ましく、１５０００以下がより好ましく、１００００以下がさらに好ましく、８０００以下がよりさらに好ましく、７０００以下が特に好ましい。前記下限値以上とすることで感度、塗膜強度、アルカリ耐性が良好となる傾向がある。また、前記上限値以下とすることで現像性や再溶解性を良好なものとすることができる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～２００００が好ましく、１０００～１５０００がより好ましく、１５００～１００００がさらに好ましく、２０００～８０００がよりさらに好ましく、２５００～７０００が特に好ましい。 The polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (A1-1) measured by gel permeation chromatography (GPC) is preferably 1000 or more, more preferably 1500 or more, still more preferably 2000 or more. 2500 or more is particularly preferable. Further, 20000 or less is preferable, 15000 or less is more preferable, 10000 or less is further preferable, 8000 or less is further preferable, and 7000 or less is particularly preferable. When the value is equal to or higher than the lower limit, the sensitivity, coating film strength, and alkali resistance tend to be good. Further, by setting the value to the upper limit or less, there is a tendency that the developability and the resolubility can be improved.
The above upper and lower limits can be combined arbitrarily. For example, 1000 to 20000 is preferable, 1000 to 15000 is more preferable, 1500 to 10000 is further preferable, 2000 to 8000 is further preferable, and 2500 to 7000 is particularly preferable.
＜アクリル共重合樹脂（Ａ２－１）、（Ａ２－２）、（Ａ２－３）、（Ａ２－４）＞
　アクリル共重合樹脂としては、例えば、日本国特開平７－２０７２１１号公報、日本国特開平８－２５９８７６号公報、日本国特開平１０－３００９２２号公報、日本国特開平１１－１４０１４４号公報、日本国特開平１１－１７４２２４号公報、日本国特開２０００－５６１１８号公報、日本国特開２００３－２３３１７９号公報、日本国特開２００７－２７０１４７号公報の各公報に記載された様々な高分子化合物を使用することができるが、好ましくは、以下の（Ａ２－１）～（Ａ２－４）の樹脂が挙げられ、中でも、（Ａ２－１）樹脂が特に好ましい。 <Acrylic copolymer resin (A2-1), (A2-2), (A2-3), (A2-4)>
Examples of the acrylic copolymer resin include Japanese Patent Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, Japanese Patent Application Laid-Open No. 11-140144, Japan. Various polymer compounds described in JP-A-11-174224, JP-A-2000-56118, JP-A-2003-233179, and JP-A-2007-270147. However, the following resins (A2-1) to (A2-4) are preferably used, and among them, the (A2-1) resin is particularly preferable.
　（Ａ２－１）：エポキシ基含有（メタ）アクリレートと、他のラジカル重合性単量体との共重合体に対し、当該共重合体が有するエポキシ基の少なくとも一部に不飽和一塩基酸を付加させてなる樹脂、あるいは当該付加反応により生じた水酸基の少なくとも一部に多塩基酸一無水物を付加させて得られる樹脂。
　（Ａ２－２）：主鎖にカルボキシ基を含有する直鎖状アルカリ可溶性樹脂。
　（Ａ２－３）：前記（Ａ２－２）樹脂のカルボキシ基部分に、エポキシ基含有不飽和化合物を付加させた樹脂。
　（Ａ２－４）：（メタ）アクリル系樹脂。 (A2-1): With respect to a polymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. A resin to be added, or a resin obtained by adding a polybasic acid monoanhydride to at least a part of the radicals generated by the addition reaction.
(A2-2): A linear alkali-soluble resin containing a carboxy group in the main chain.
(A2-3): A resin in which an epoxy group-containing unsaturated compound is added to the carboxy group portion of the (A2-2) resin.
(A2-4): (Meta) acrylic resin.
　本発明における感光性樹脂組成物は、感度の観点から、エチレン性不飽和基を含有するアルカリ可溶性樹脂として（Ａ１－１）、（Ａ２－１）、（Ａ２－３）の少なくとも何れかを含むことがさらに好ましい。本発明における感光性樹脂組成物は、表面硬化性の観点から、エチレン性不飽和基を含有するアルカリ可溶性樹脂としてエポキシ（メタ）アクリレート樹脂である（Ａ１－１）を含むことが特に好ましい。 The photosensitive resin composition in the present invention contains at least one of (A1-1), (A2-1), and (A2-3) as an alkali-soluble resin containing an ethylenically unsaturated group from the viewpoint of sensitivity. Is even more preferable. From the viewpoint of surface curability, the photosensitive resin composition in the present invention particularly preferably contains an epoxy (meth) acrylate resin (A1-1) as an alkali-soluble resin containing an ethylenically unsaturated group.
　（Ａ）アルカリ可溶性樹脂の含有割合は、特に限定されないが、感光性樹脂組成物の全固形分に対して、通常５質量％以上、好ましくは１０質量％以上、より好ましくは１５質量％以上であり、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは５０質量％以下、さらに好ましくは３０質量％以下、特に好ましくは２５質量％以下である。前記下限値以上とすることで未露光部分の現像液に対する溶解性が良好となる傾向がある。また、前記上限値以下とすることで露光部への現像液の過剰な浸透を抑制することができ、画像のシャープ性や密着性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、５～９０質量％が好ましく、５～７０質量％がより好ましく、１０～５０質量％がさらに好ましく、１０～３０質量％がよりさらに好ましく、１５～２５質量％が特に好ましい。
　また、上述のように、本発明における感光性樹脂組成物が、（Ａ）アルカリ可溶性樹脂として、その他のアルカリ可溶性樹脂を含有する場合、前述の（Ａ１－１）、（Ａ２－１）、（Ａ２－２）、（Ａ２－３）及び（Ａ２－４）の少なくとも１種を含むことが好ましい。
　本発明における感光性樹脂組成物が、その他のアルカリ可溶性樹脂を含む場合、その含有割合は、レジストパターニングの観点から（Ａ）アルカリ可溶性樹脂の合計に対して、３０質量％以下が好ましく、２０質量％以下がより好ましく、１０質量％以下がさらに好ましく、含まなくてもよい。 The content ratio of the alkali-soluble resin (A) is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more with respect to the total solid content of the photosensitive resin composition. It is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less. By setting the value to the lower limit or more, the solubility of the unexposed portion in the developing solution tends to be good. Further, by setting the value to the upper limit or less, excessive penetration of the developing solution into the exposed portion can be suppressed, and the sharpness and adhesion of the image tend to be improved.
The above upper and lower limits can be combined arbitrarily. For example, 5 to 90% by mass is preferable, 5 to 70% by mass is more preferable, 10 to 50% by mass is further preferable, 10 to 30% by mass is further preferable, and 15 to 25% by mass is particularly preferable.
Further, as described above, when the photosensitive resin composition in the present invention contains another alkali-soluble resin as the (A) alkali-soluble resin, the above-mentioned (A1-1), (A2-1), ( It is preferable to contain at least one of A2-2), (A2-3) and (A2-4).
When the photosensitive resin composition in the present invention contains other alkali-soluble resin, the content ratio thereof is preferably 30% by mass or less, preferably 20% by mass, based on the total amount of (A) alkali-soluble resin from the viewpoint of resist patterning. % Or less is more preferable, and 10% by mass or less is further preferable, and it may not be contained.
＜（Ｂ）光重合性モノマー＞
　本発明における感光性樹脂組成物は、感度等の点から（Ｂ）光重合性モノマーを含有する。
　（Ｂ）光重合性モノマーとしては、分子内にエチレン性不飽和基を少なくとも１個有する化合物（以下、「エチレン性単量体」と称することがある。）を挙げることができる。具体的には、例えば、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、アクリロニトリル、スチレン、及びエチレン性不飽和結合を１個有するカルボン酸と、多価又は１価アルコールのエステルが挙げられる。 <(B) Photopolymerizable monomer>
The photosensitive resin composition in the present invention contains (B) a photopolymerizable monomer from the viewpoint of sensitivity and the like.
Examples of the (B) photopolymerizable monomer include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter, may be referred to as “ethylenic monomer”). Specific examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, and carboxylic acids having one ethylenically unsaturated bond, and esters of polyvalent or monovalent alcohols. ..
　（Ｂ）光重合性モノマーとしては、特に、１分子中にエチレン性不飽和基を２個以上有する多官能エチレン性単量体を使用することが好ましい。多官能エチレン性単量体におけるエチレン性不飽和基の数は通常２個以上、好ましくは３個以上、より好ましくは４個以上、さらに好ましくは５個以上、特に好ましくは６個以上、また通常１０個以下、好ましくは８個以下である。前記下限値以上とすることで感光性樹脂組成物が高感度となる傾向があり、また、前記上限値以下とすることで重合時の硬化収縮が小さくなる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２～１０個が好ましく、３～１０個がより好ましく、４～１０個がさらに好ましく、５～８個がよりさらに好ましく、６～８個が特に好ましい。
　多官能エチレン性単量体の例としては、例えば、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルが挙げられる。 As the photopolymerizable monomer (B), it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is usually 2 or more, preferably 3 or more, more preferably 4 or more, still more preferably 5 or more, particularly preferably 6 or more, and usually. The number is 10 or less, preferably 8 or less. When it is at least the above lower limit value, the photosensitive resin composition tends to have high sensitivity, and when it is at least the above upper limit value, the curing shrinkage during polymerization tends to be small.
The above upper and lower limits can be combined arbitrarily. For example, 2 to 10 pieces are preferable, 3 to 10 pieces are more preferable, 4 to 10 pieces are further preferable, 5 to 8 pieces are more preferable, and 6 to 8 pieces are particularly preferable.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a polyhydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.
　脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル、これら例示化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル、同様にイタコネートに代えたイタコン酸エステル、クロネートに代えたクロトン酸エステルもしくはマレエートに代えたマレイン酸エステルが挙げられる。 Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, acrylic acid ester of aliphatic polyhydroxy compounds such as glycerol acrylate, methacrylic acid in which the acrylate of these exemplary compounds is replaced with methacrylate. Examples thereof include esters, itaconic acid esters in place of itaconate, crotonic acid esters in place of clonate, and maleic acid esters in which maleate is replaced.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステルが挙げられる。
　多塩基性カルボン酸及び不飽和カルボン酸と、多価ヒドロキシ化合物のエステル化反応により得られるエステルとしては必ずしも単一物ではないが、代表的な具体例を挙げれば、アクリル酸、フタル酸、及びエチレングリコールの縮合物、アクリル酸、マレイン酸、及びジエチレングリコールの縮合物、メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物、アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物が挙げられる。 Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include acrylic acid esters and methacrylics of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogalloltriacrylate. Acid esters can be mentioned.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single substance, but typical specific examples include acrylic acid, phthalic acid, and Examples thereof include a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid, and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, and a condensate of acrylic acid, adipic acid, butanediol and glycerin.
　その他、本発明に用いられる多官能エチレン性単量体の例としては、例えば、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物とヒドロキシ（メタ）アクリレート又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物が有用である。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, for example, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted. Urethane (meth) acrylates such as those obtained by the above; epoxy acrylates such as an addition reaction product of a polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; phthal Allyl esters such as diallylic acid; vinyl group-containing compounds such as divinylphthalate are useful.
These may be used alone or in combination of two or more.
　（Ｂ）光重合性モノマーの含有割合は、特に限定されないが、感光性樹脂組成物の全固形分に対して、通常９０質量％以下、好ましくは７０質量％以下、より好ましくは５０質量％以下、さらに好ましくは３０質量％以下、よりさらに好ましくは２０質量％以下、特に好ましくは１０質量％以下である。光重合性モノマーの含有量が上記上限値以下であることで、露光部への現像液の浸透性が適度となり良好な画像を得ることができる傾向にある。光重合性モノマー（ｂ）の含有量は、通常１質量％以上、好ましくは５質量％以上である。上記下限値以上であることで、紫外線照射による光硬化を向上させるとともにアルカリ現像性も良好となる傾向にある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～９０質量％が好ましく、１～７０質量％がより好ましく、１～５０質量％がさらに好ましく、５～３０質量％がよりさらに好ましく、５～２０質量％がことさら好ましく、５～１０質量％が特に好ましい。 The content ratio of the photopolymerizable monomer (B) is not particularly limited, but is usually 90% by mass or less, preferably 70% by mass or less, more preferably 50% by mass or less, based on the total solid content of the photosensitive resin composition. It is more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less. When the content of the photopolymerizable monomer is not more than the above upper limit value, the permeability of the developing solution to the exposed portion becomes appropriate, and a good image tends to be obtained. The content of the photopolymerizable monomer (b) is usually 1% by mass or more, preferably 5% by mass or more. When it is at least the above lower limit value, the photocuring due to ultraviolet irradiation is improved and the alkali developability tends to be good.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 90% by mass is preferable, 1 to 70% by mass is more preferable, 1 to 50% by mass is further preferable, 5 to 30% by mass is further preferable, and 5 to 20% by mass is particularly preferable. Mass% is particularly preferred.
＜（Ｃ）光重合開始剤＞
　本発明における感光性樹脂組成物は（Ｃ）光重合開始剤を含有する。光重合開始剤は光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分である。必要に応じて増感色素等の付加剤を添加して使用してもよい。 <(C) Photopolymerization Initiator>
The photosensitive resin composition in the present invention contains (C) a photopolymerization initiator. The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a sensitizing dye may be added and used.
　光重合開始剤としては、例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号各公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体、ハロメチル－ｓ－トリアジン誘導体、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体；日本国特開２０００－８００６８号公報、日本国特開２００６－３６７５０号公報等に記載されているオキシムエステル誘導体が挙げられる。 As the photopolymerization initiator, for example, a metallocene compound containing a titanosen compound described in JP-A-59-152396 and JP-A-61-151197 of Japan; Japanese Patent Application Laid-Open No. 2000-56118. Hexaaryl-biimidazole derivative according to Japanese Patent Application Laid-Open No. 10-39503, halomethylated oxadiazole derivative, halomethyl-s-triazine derivative, N-aryl-α-amino acids such as N-phenylglycine, N. -Radical activators such as aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, etc. Examples thereof include the oxime ester derivative described in 1.
　チタノセン誘導体類としては、例えば、ジシクロペンタジエニルチタニウムジクロライド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニ－１－イル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニ－１－イル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロ－１－イル）－フェニ－１－イル〕が挙げられる。 Examples of titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoropheni-1-yl). ), Dicyclopentadienyl Titanium Bis (2,3,5,6-Tetrafluoropheni-1-yl), Dicyclopentadienyl Titanium Bis (2,4,6-Trifluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopentadienyl) Titanium Bis (2,3,4,5,6-pentafluoropheni-1-yl), di (methylcyclopentadienyl) titanium bis (2,6-difluoropheni-1-yl), dicyclopentadienyl titanium [ 2,6-Di-fluoro-3- (pyro-1-yl) -pheni-1-yl].
　ビイミダゾール誘導体類としては、例えば、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフエニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフエニル）－４，５－ジフェニルイミダゾール２量体が挙げられる。 Examples of the biimidazole derivatives include 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole. Dimeric, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxy) Phenyl) -4,5-diphenylimidazole dimer can be mentioned.
　ハロメチル化オキサジアゾール誘導体類としては、例えば、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６”－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾールが挙げられる。 Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[β- (2'-). Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole can be mentioned.
　ハロメチル－ｓ－トリアジン誘導体類としては、例えば、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジンが挙げられる。 Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-Triazine can be mentioned.
　α－アミノアルキルフェノン誘導体類としては、例えば、２－メチル－１〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル)ブタン－１－オン、４－ジメチルアミノエチルベンゾエ－ト、４－ジメチルアミノイソアミルベンゾエ－ト、４－ジエチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン、２－エチルヘキシル－１，４－ジメチルアミノベンゾエート、２，５－ビス（４－ジエチルアミノベンザル)シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコンが挙げられる。 Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-). Morphorinophenyl) Butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4 -Dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone can be mentioned.
　光重合開始剤としては、特に、感度の点でオキシム誘導体類（オキシムエステル系化合物及びケトオキシムエステル系化合物）が有用である。オキシム誘導体類の中でも、基板との密着性の観点から、オキシムエステル系化合物が好ましい。フェノール性水酸基を含むアルカリ可溶性樹脂を用いる場合は、感度の点で不利になる場合がある。 As the photopolymerization initiator, oxime derivatives (oxime ester-based compounds and keto-oxime ester-based compounds) are particularly useful in terms of sensitivity. Among the oxime derivatives, oxime ester compounds are preferable from the viewpoint of adhesion to the substrate. When an alkali-soluble resin containing a phenolic hydroxyl group is used, it may be disadvantageous in terms of sensitivity.
　オキシムエステル系化合物の光重合開始剤は、その構造の中に紫外線を吸収する構造と光エネルギーを伝達する構造とラジカルを発生する構造を併せ持っているために、少量で感度が高く、かつ熱反応に対しては安定であり、少量で高感度な感光性樹脂組成物の設計が可能である。特に、露光光源のｉ線（３６５ｎｍ）に対する光吸収性の観点から、置換されていてもよいカルバゾリル基（置換されていてもよいカルバゾール環を有する基）を含有するオキシムエステル系化合物の場合に、この構造特性が良好に発現され、より好ましい。現在、市場では、遮光度が高く、薄膜なブラックマトリックスが要求されており、顔料濃度も、ますます大きくなっている。このような状況においては、特に有効である。 The photopolymerization initiator of an oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, so that it is highly sensitive in a small amount and has a thermal reaction. It is possible to design a photosensitive resin composition that is stable and highly sensitive in a small amount. In particular, in the case of an oxime ester-based compound containing a optionally substituted carbazolyl group (a group having a optionally substituted carbazole ring) from the viewpoint of light absorption of an exposure light source for i-ray (365 nm). This structural property is well expressed and is more preferable. Currently, the market demands a black matrix with a high degree of shading and a thin film, and the pigment concentration is also increasing. It is especially effective in such situations.
　オキシムエステル系化合物としては、下記一般式（２２）で示される構造部分を含む化合物が挙げられ、好ましくは、下記一般式（２３）で示されるオキシムエステル系化合物が挙げられる。 Examples of the oxime ester compound include a compound containing a structural portion represented by the following general formula (22), and preferably an oxime ester compound represented by the following general formula (23).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（２２）中、Ｒ22は、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数３～２０のアルコキシカルボニルアルカノイル基、炭素数８～２０のフェノキシカルボニルアルカノイル基、炭素数３～２０のヘテロアリ－ルオキシカルボニルアルカノイル基、炭素数２～１０のアミノアルキルカルボニル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、又は炭素数７～２０のアリールオキシカルボニル基を示す。 In the above formula (22), R 22 may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, and a carbon number of carbon atoms. Cyclo alkanoyl group of 3 to 8, alkoxycarbonyl alkanoyl group of 3 to 20 carbon atoms, phenoxycarbonyl alkanoyl group of 8 to 20 carbon atoms, heteroallyloxycarbonyl alkanoyl group of 3 to 20 carbon atoms, 2 to 10 carbon atoms An aminoalkylcarbonyl group, an allylloyl group having 7 to 20 carbon atoms, a heteroallyloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms is shown.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（２３）中、Ｒ21aは、水素、またはそれぞれ置換されていてもよい、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、又は炭素数１～１０のシクロアルキルアルキル基を示す。
　Ｒ21bは芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。 In formula (23), R 21a is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroarylalkyl group having 1 to 20 carbon atoms, which may be substituted with hydrogen, respectively. An alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group or a heteroarylthioalkyl group having 1 to 20 carbon atoms, and an aminoalkyl group having 1 to 20 carbon atoms. , Alkyloyl group with 2 to 12 carbon atoms, alkenoyl group with 3 to 25 carbon atoms, cycloalkanoyl group with 3 to 8 carbon atoms, allylloyl group with 7 to 20 carbon atoms, heteroallyloyl group with 1 to 20 carbon atoms, carbon An alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown.
R 21b represents any substituent, including aromatic or heteroaromatic rings.
　なお、Ｒ21aはＲ21bと共に環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。
　Ｒ22aは、上記式（２２）のおけるＲ22と同様の基を示す。
　上記一般式（２２）におけるＲ22及び上記一般式（２３）におけるＲ22aとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基が挙げられる。 In addition, R 21a may form a ring together with R 21b , and the linking group thereof may be an alkylene group having 1 to 10 carbon atoms and a polyethylene group (-(CH = CH) r ), each of which may have a substituent. -), Polyethynylene group (-(C≡C) r- ) or a group composed of a combination thereof can be mentioned (where r is an integer of 0 to 3).
R 22a represents the same group as R 22 in the above formula (22).
The R 22 in the general formula (22) and the R 22a in the general formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group of.
　上記一般式（２３）におけるＲ21aとしては、好ましくは無置換のメチル基、エチル基、プロピル基などの直鎖アルキル基又はシクロアルキルアルキル基や、Ｎ－アセチル－Ｎ－アセトキシアミノ基で置換されたプロピル基が挙げられる。
　また、上記一般式（２３）におけるＲ21bとしては、好ましくは置換されていてもよいカルバゾリル基、置換されていてもよいチオキサントニル基、置換されていてもよいフェニルスルフィド基が挙げられる。 The R 21a in the above general formula (23) is preferably substituted with an unsubstituted linear alkyl group such as a methyl group, an ethyl group or a propyl group, a cycloalkylalkyl group, or an N-acetyl-N-acetoxyamino group. Propyl group can be mentioned.
Further, examples of R 21b in the above general formula (23) include a carbazolyl group which may be substituted, a thioxanthonyl group which may be substituted, and a phenylsulfide group which may be substituted.
　オキシムエステル系化合物の光重合開始剤としては、上記一般式（２３）におけるＲ21bが、置換されていてもよいカルバゾリル基であるものが、前述の理由からより好ましい。さらに、置換されていてもよい炭素数６～２５のアリール基、置換されていてもよい炭素数７～２５のアリールカルボニル基、置換されていてもよい炭素数５～２５のヘテロアリール基、置換されていてもよい炭素数６～２５のヘテロアリールカルボニル基、及びニトロ基からなる群から選ばれる少なくとも１種の基を有するカルバゾール基が好ましい。特に、ベンゾイル基、トルオイル基、ナフトイル基、チエニルカルボニル基、及びニトロ基からなる群から選ばれる少なくとも１種の基を有するカルバゾリル基が好ましい。また、これらの基はカルバゾリル基の３位に結合していることが望ましい。 As the photopolymerization initiator of the oxime ester compound, one in which R 21b in the above general formula (23) is a carbazolyl group which may be substituted is more preferable for the above-mentioned reason. Further, an aryl group having 6 to 25 carbon atoms which may be substituted, an arylcarbonyl group having 7 to 25 carbon atoms which may be substituted, a heteroaryl group having 5 to 25 carbon atoms which may be substituted, and a substituted moiety. A carbazole group having at least one group selected from the group consisting of a heteroarylcarbonyl group having 6 to 25 carbon atoms and a nitro group may be preferable. In particular, a carbazolyl group having at least one group selected from the group consisting of a benzoyl group, a toluoil group, a naphthoyl group, a thienylcarbonyl group, and a nitro group is preferable. Further, it is desirable that these groups are bonded to the 3-position of the carbazolyl group.
　このようなオキシムエステル系化合物の光重合開始剤の市販品として、ＢＡＳＦ社製のＯＸＥ－０２、常州強力電子社製のＴＲ－ＰＢＧ－３０４やＴＲ－ＰＢＧ－３１４などがある。 Commercially available products of such photopolymerization initiators of oxime ester compounds include OXE-02 manufactured by BASF, TR-PBG-304 and TR-PBG-314 manufactured by Joshu Power Electronics Co., Ltd.
　本発明に好適なオキシムエステル系化合物の光重合開始剤として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 Specific examples of the photopolymerization initiator of the oxime ester compound suitable for the present invention include the compounds exemplified below, but the present invention is not limited to these compounds.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　ケトオキシムエステル系化合物としては、下記一般式（２４）で示される構造部分を含む化合物が挙げられ、好ましくは、下記一般式（２５）で示されるケトオキシムエステル系化合物が挙げられる。 Examples of the ketooxime ester compound include a compound containing a structural portion represented by the following general formula (24), and preferably a ketooxime ester compound represented by the following general formula (25).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　上記一般式（２４）において、Ｒ24は、前記一般式（２２）におけるＲ22と同義である。 In the general formula (24), R 24 is synonymous with R 22 in the general formula (22).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記一般式（２５）において、Ｒ23aは、それぞれ置換されていてもよい、フェニル基、炭素数１～２０のアルキル基、炭素数２～２５のアルケニル基、炭素数１～２０のヘテロアリールアルキル基、炭素数３～２０のアルコキシカルボニルアルキル基、炭素数８～２０のフェノキシカルボニルアルキル基、炭素数２～２０のアルキルチオアルキル基、炭素数１～２０のヘテロアリールオキシカルボニルアルキル基もしくはヘテロアリールチオアルキル基、炭素数１～２０のアミノアルキル基、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基、炭素数１～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、又は炭素数１～１０のシクロアルキルアルキル基を示す。 In the above general formula (25), R 23a may be substituted with a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, and a heteroarylalkyl group having 1 to 20 carbon atoms, respectively. Group, alkoxycarbonylalkyl group with 3 to 20 carbon atoms, phenoxycarbonylalkyl group with 8 to 20 carbon atoms, alkylthioalkyl group with 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl group with 1 to 20 carbon atoms or heteroarylthio Alkyl group, aminoalkyl group with 1 to 20 carbon atoms, alkanoyl group with 2 to 12 carbon atoms, alkenoyl group with 3 to 25 carbon atoms, cycloalkanoyl group with 3 to 8 carbon atoms, allylloyl group with 7 to 20 carbon atoms, A heteroarylloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or a cycloalkylalkyl group having 1 to 10 carbon atoms is shown.
　Ｒ23bは芳香環あるいはヘテロ芳香環を含む任意の置換基を示す。
　なお、Ｒ23aはＲ23bと共に環を形成してもよく、その連結基は、それぞれ置換基を有していてもよい炭素数１～１０のアルキレン基、ポリエチレン基（－（ＣＨ＝ＣＨ）r－）、ポリエチニレン基（－（Ｃ≡Ｃ）r－）あるいはこれらを組み合わせてなる基が挙げられる（なお、ｒは０～３の整数である。）。 R 23b represents any substituent, including aromatic or heteroaromatic rings.
In addition, R 23a may form a ring together with R 23b , and the linking group thereof may be an alkylene group having 1 to 10 carbon atoms and a polyethylene group (-(CH = CH) r ), each of which may have a substituent. -), Polyethynylene group (-(C≡C) r- ) or a group composed of a combination thereof can be mentioned (where r is an integer of 0 to 3).
　Ｒ24aは、それぞれ置換されていてもよい、炭素数２～１２のアルカノイル基、炭素数３～２５のアルケノイル基、炭素数４～８のシクロアルカノイル基、炭素数７～２０のベンゾイル基、炭素数３～２０のヘテロアリーロイル基、炭素数２～１０のアルコキシカルボニル基、炭素数７～２０のアリールオキシカルボニル基、炭素数２～２０のヘテロアリール基、又は炭素数２～２０のアルキルアミノカルボニル基を表す。
　上記一般式（２４）におけるＲ24及び上記一般式（２５）におけるＲ24aとしては、好ましくは、炭素数２～１２のアルカノイル基、炭素数１～２０のヘテロアリールアルカノイル基、炭素数３～８のシクロアルカノイル基、炭素数７～２０のアリーロイル基が挙げられる。 R 24a may be substituted with an alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, a benzoyl group having 7 to 20 carbon atoms, and carbon. A heteroallyloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylamino having 2 to 20 carbon atoms. Represents a carbonyl group.
The R 24 in the general formula (24) and the R 24a in the general formula (25) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and 3 to 8 carbon atoms. Cycloalkanoyl group and allyloyl group having 7 to 20 carbon atoms can be mentioned.
　上記一般式（２５）におけるＲ23aとしては、好ましくは無置換のエチル基、プロピル基、ブチル基や、メトキシカルボニル基で置換されたエチル基またはプロピル基が挙げられる。
　また、上記一般式（２５）におけるＲ23bとしては、好ましくは置換されていてもよいカルバゾイル基、置換されていてもよいフェニルスルフィド基が挙げられる。
　本発明に好適なケトオキシムエステル系化合物として具体的には、以下に例示されるような化合物が挙げられるが、何らこれらの化合物に限定されるものではない。 The R 23a in the above general formula (25) preferably includes an unsubstituted ethyl group, a propyl group, a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
Further, examples of R 23b in the above general formula (25) include a optionally substituted carbazoyl group and an optionally substituted phenylsulfide group.
Specific examples of the ketooxime ester-based compound suitable for the present invention include, but are not limited to, the compounds exemplified below.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　このようなケトオキシムエステル系化合物の光重合開始剤の市販品として、ＢＡＳＦ社製のＯＸＥ－０１、常州強力電子社製のＴＲ－ＰＢＧ－３０５などがある。 Commercially available products of such photopolymerization initiators for ketooxime ester compounds include OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Joshu Strong Electronics.
　これらのオキシム及びケトオキシムエステル系化合物は、それ自体公知の化合物であり、例えば、日本国特開２０００－８００６８号公報や、日本国特開２００６－３６７５０号公報に記載されている一連の化合物の一種である。
　上記光重合開始剤は１種を単独で用いてもよく、２種以上を併用してもよい。 These oxime and ketooxyester compounds are known compounds themselves, and are, for example, a series of compounds described in Japanese Patent Laid-Open No. 2000-80068 and Japanese Patent Application Laid-Open No. 2006-36750. It is a kind.
The above photopolymerization initiator may be used alone or in combination of two or more.
　その他に、例えば、ベンゾインメチルエーテル、ベンゾインフェニルエーテル、ベンゾインイソブチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインアルキルエーテル類；２－メチルアントラキノン、２－エチルアントラキノン、２－ｔ－ブチルアントラキノン、１－クロロアントラキノン等のアントラキノン誘導体類；ベンゾフェノン、ミヒラーズケトン、２－メチルベンゾフェノン、３－メチルベンゾフェノン、４－メチルベンゾフェノン、２－クロロベンゾフェノン、４－ブロモベンゾフェノン、２－カルボキシベンゾフェノン等のベンゾフェノン誘導体類；２，２－ジメトキシ－２－フェニルアセトフェノン、２，２－ジエトキシアセトフェノン、１－ヒドロキシシクロへキシルフェニルケトン、α－ヒドロキシ－２－メチルフェニルプロパノン、１－ヒドロキシ－１－メチルエチル－（ｐ－イソプロピルフェニル）ケトン、１－ヒドロキシ－１－（ｐ－ドデシルフェニル）ケトン、２－メチル－（４’－メチルチオフェニル）－２－モルホリノ－１－プロパノン、１，１，１－トリクロロメチル－（ｐ－ブチルフェニル）ケトン等のアセトフェノン誘導体類；チオキサントン、２－エチルチオキサントン、２－イソプロピルチオキサントン、２－クロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン等のチオキサントン誘導体類；ｐ－ジメチルアミノ安息香酸エチル、ｐ－ジエチルアミノ安息香酸エチル等の安息香酸エステル誘導体類；９－フェニルアクリジン、９－（ｐ－メトキシフェニル）アクリジン等のアクリジン誘導体類；９，１０－ジメチルベンズフェナジン等のフェナジン誘導体類；ベンズアンスロン等のアンスロン誘導体類が挙げられる。
　これらの光重合開始剤の中では、前述の理由からオキシムエステル誘導体類が特に好ましい。 In addition, for example, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and the like. Anthraquinone derivatives; benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2,2-dimethoxy-2 -Phenylacetphenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1, -Hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanol, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, etc. Acetphenone derivatives; thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diisopropylthioxanthone; p- Ethyl benzoate ester derivatives such as ethyl dimethylaminobenzoate and ethyl p-diethylaminobenzoate; aclysine derivatives such as 9-phenylaclysine and 9- (p-methoxyphenyl) acrydin; phenazines such as 9,10-dimethylbenzphenazine. Derivatives; Examples thereof include anthrone derivatives such as benzansuron.
Among these photopolymerization initiators, oxime ester derivatives are particularly preferable for the above-mentioned reasons.
＜増感色素＞
　光重合開始剤には、必要に応じて、感応感度を高める目的で、画像露光光源の波長に応じた増感色素を併用させることができる。これら増感色素としては、例えば、日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、その他、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素を挙げることができる。 <Sensitizer>
If necessary, the photopolymerization initiator may be used in combination with a sensitizing dye according to the wavelength of the image exposure light source for the purpose of increasing the sensitivity. Examples of these sensitizing dyes include the xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Laid-Open No. 4-219756, Japanese Patent Application Laid-Open No. 3-239703, and Japanese Patent Application Laid-Open No. 5-239703. A coumarin dye having a heterocycle described in Japanese Patent Application Laid-Open No. 289335, a 3-ketocoumarin compound described in Japanese Patent Application Laid-Open No. 3-239703, Japanese Patent Application Laid-Open No. 5-289335, and Japanese Patent Application Laid-Open No. 6-19240. Japanese Patent Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Publication No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Japanese Patent Application Laid-Open No. 58-15503, Japanese Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-56403 Dialkylaminobenzene described in JP-A-69, JP-A-57-16888, JP-A-5-107761, JP-A, JP-A-5-210240, JP-A, JP-A-4-288818, Japan. Pigments with a skeleton can be mentioned.
　これらの増感色素のうち、アミノ基含有増感色素が好ましく、アミノ基及びフェニル基を同一分子内に有する化合物がより好ましい。例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物がさらに好ましく、４，４’－ジアルキルアミノベンゾフェノンが特に好ましい。
　増感色素は１種を単独で用いてもよく、２種以上を併用してもよい。 Among these sensitizing dyes, amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diamino. Benzophenone compounds such as benzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (P-Dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- ( p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (P-Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidin Such as p-dialkylaminophenyl group-containing compound is more preferable, and 4,4'-dialkylaminobenzophenone is particularly preferable.
One type of sensitizing dye may be used alone, or two or more types may be used in combination.
　（Ｃ）光重合開始剤の含有量は、特に限定されないが、感光性樹脂組成物の全固形分に対して、通常１質量％以上、好ましくは２質量％以上、より好ましくは３質量以上、さらに好ましくは４質量％以上であり、通常３０質量％以下、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下、特に好ましくは８質量％以下である。前記下限値以上とすることで感度が向上する傾向がある。また、前記上限値以下とすることで未露光部分の現像液に対する溶解性が向上する傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～３０質量％が好ましく、１～２０質量％がより好ましく、２～１５質量％がさらに好ましく、３～１０質量％がよりさらに好ましく、４～８質量％が特に好ましい。 The content of the photopolymerization initiator (C) is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, based on the total solid content of the photosensitive resin composition. It is more preferably 4% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less. Sensitivity tends to improve when the value is equal to or higher than the lower limit. Further, when the value is not more than the upper limit, the solubility of the unexposed portion in the developing solution tends to be improved.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 30% by mass is preferable, 1 to 20% by mass is more preferable, 2 to 15% by mass is further preferable, 3 to 10% by mass is further preferable, and 4 to 8% by mass is particularly preferable.
　増感色素を用いる場合、感光性樹脂組成物中に占める増感色素の配合割合は感光性樹脂組成物中の全固形分中、通常０～２０質量％、好ましくは０～１５質量％、さらに好ましくは０～１０質量％である。 When the sensitizing dye is used, the blending ratio of the sensitizing dye in the photosensitive resin composition is usually 0 to 20% by mass, preferably 0 to 15% by mass, and further, in the total solid content in the photosensitive resin composition. It is preferably 0 to 10% by mass.
＜（Ｄ）色材＞
　本発明における感光性樹脂組成物は、カラーフィルターの画素、ブラックマトリックス、着色スペーサーの形成等に用いられる場合には、（Ｄ）色材を含有するのが好ましい。色材は、本発明における感光性樹脂組成物を着色するものをいう。色材としては、染料や顔料が使用できるが、耐熱性、耐光性等の点から、顔料が好ましい。 <(D) Color material>
When the photosensitive resin composition in the present invention is used for forming pixels of a color filter, a black matrix, a colored spacer, or the like, it is preferable to contain (D) a coloring material. The coloring material refers to a material that colors the photosensitive resin composition in the present invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.
　顔料としては青色顔料、緑色顔料、赤色顔料、黄色顔料、紫色顔料、オレンジ顔料、ブラウン顔料、黒色顔料等各種の色の顔料を使用することができる。また、その構造としては例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系の有機顔料の他に種々の無機顔料も利用可能である。 As the pigment, pigments of various colors such as blue pigment, green pigment, red pigment, yellow pigment, purple pigment, orange pigment, brown pigment and black pigment can be used. Further, as the structure, for example, various inorganic pigments can be used in addition to azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolenone-based, dioxazine-based, indanthrone-based, and perylene-based organic pigments. Is.
　以下に、本発明に使用できる顔料の具体例をピグメントナンバーで示す。なお、以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。
　赤色顔料としては、例えば、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１６８、１７７、２０２、２０６、２０７、２０９、２２４、２４２、２５４、より好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。 Specific examples of pigments that can be used in the present invention are shown below by pigment numbers. The terms such as "CI Pigment Red 2" listed below mean the color index (CI).
Examples of the red pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 can be mentioned. Among these, preferably C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, 254 can be mentioned.
　青色顔料としては、例えば、Ｃ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８、７９を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、６０、より好ましくはＣ．Ｉ．ピグメントブルー１５：６、６０を挙げることができる。 Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, preferably C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, more preferably C.I. I. Pigment Blue 15: 6, 60 can be mentioned.
　緑色顔料としては、例えば、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５、５８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６、５８を挙げることができる。 Examples of the green pigment include C.I. I. Pigment Greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be mentioned. Among these, preferably C.I. I. Pigment Greens 7, 36 and 58 can be mentioned.
　黄色顔料としては、例えば、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、より好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。 Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,41,42,43,48,53,55,61,62,62: 1,63,65,73,74,75,81,83,87,93,94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
　オレンジ顔料としては、例えば、Ｃ．Ｉ．ピグメントオレンジ１、２、５、１３、１６、１７、１９、２０、２１、２２、２３、２４、３４、３６、３８、３９、４３、４６、４８、４９、６１、６２、６４、６５、６７、６８、６９、７０、７１、７２、７３、７４、７５、７７、７８、７９を挙げることができる。この中でも、好ましくは、Ｃ．Ｉ．ピグメントオレンジ３８、６４、７１を挙げることができる。 Examples of the orange pigment include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, preferably, C.I. I. Pigment Orange 38, 64, 71 can be mentioned.
　紫色顔料としては、例えば、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。この中でも、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、２９、より好ましくはＣ．Ｉ．ピグメントバイオレット２３、２９を挙げることができる。 As the purple pigment, for example, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, preferably C.I. I. Pigment Violet 19, 23, 29, more preferably C.I. I. Pigment Violet 23, 29 can be mentioned.
　本発明における感光性樹脂組成物が、カラーフィルターの樹脂ブラックマトリックス用感光性樹脂組成物である場合、（Ｄ）色材としては、黒色の色材を用いることができる。黒色色材は、黒色色材単独としてもよく、赤、緑、青色色材等の混合としてもよい。また、これら色材は無機又は有機の顔料、染料の中から適宜選択することができる。
　黒色色材を調製するために混合使用可能な色材としては、例えば、ビクトリアピュアブルー（４２５９５）、オーラミンＯ（４１０００）、カチロンブリリアントフラビン（ベーシック１３）、ローダミン６ＧＣＰ（４５１６０）、ローダミンＢ（４５１７０）、サフラニンＯＫ７０：１００（５０２４０）、エリオグラウシンＸ（４２０８０）、Ｎｏ．１２０／リオノールイエロー（２１０９０）、リオノールイエローＧＲＯ（２１０９０）、シムラーファーストイエロー８ＧＦ（２１１０５）、ベンジジンイエロー４Ｔ－５６４Ｄ（２１０９５）、シムラーファーストレッド４０１５（１２３５５）、リオノールレッド７Ｂ４４０１（１５８５０）、ファーストゲンブルーＴＧＲ－Ｌ（７４１６０）、リオノールブルーＳＭ（２６１５０）、リオノールブルーＥＳ（ピグメントブルー１５：６）、リオノーゲンレッドＧＤ（ピグメントレッド１６８）、リオノールグリーン２ＹＳ（ピグメントグリーン３６）が挙げられる（なお、上記の（　）内の数字は、カラーインデックス（Ｃ．Ｉ．）を意味する。）。 When the photosensitive resin composition in the present invention is a photosensitive resin composition for a resin black matrix of a color filter, a black coloring material can be used as the (D) coloring material. The black color material may be a black color material alone or may be a mixture of red, green, blue color materials and the like. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes.
Examples of the color materials that can be mixed and used to prepare the black color material include Victoria Pure Blue (42595), Auramine O (41000), Cachilon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), and Rhodamine B ( 45170), Safranin OK70: 100 (50240), Eriograusin X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Simler First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Simler First Red 4015 (12355), Lionol Red 7B4401 (15850), Firstgen Blue TGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15: 6), Lionor Gen Red GD (Pigment Red 168), Lionor Green 2YS (Pigment Green 36) (Note that the numbers in () above mean the color index (CI)).
　さらに他の混合使用可能な顔料についてＣ．Ｉ．ナンバーにて示すと、例えば、Ｃ．Ｉ．黄色顔料２０、２４、８６、９３、１０９、１１０、１１７、１２５、１３７、１３８、１４７、１４８、１５３、１５４、１６６、Ｃ．Ｉ．オレンジ顔料３６、４３、５１、５５、５９、６１、６４、Ｃ．Ｉ．赤色顔料９、９７、１２２、１２３、１４９、１６８、１７７、１８０、１９２、２１５、２１６、２１７、２２０、２２３、２２４、２２６、２２７、２２８、２４０、２５４、Ｃ．Ｉ．バイオレット顔料１９、２３、２９、３０、３７、４０、５０、Ｃ．Ｉ．青色顔料１５、１５：１、１５：４、２２、６０、６４、Ｃ．Ｉ．緑色顔料７、Ｃ．Ｉ．ブラウン顔料２３、２５、２６を挙げることができる。 Regarding other pigments that can be mixed and used, C.I. I. Indicated by number, for example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, 64, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Brown pigments 23, 25 and 26 can be mentioned.
　単独使用可能な黒色色材としては、例えば、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、アニリンブラック、シアニンブラック、チタンブラック、ペリレンブラック、ラクタムブラックが挙げられる。
　これらの（Ｄ）色材の中で黒色の色材を用いる場合には、遮光率、画像特性の観点からカーボンブラックが好ましい。カーボンブラックの例としては、以下のようなカーボンブラックが挙げられる。 Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, perylene black, and lactam black.
When a black color material is used among these (D) color materials, carbon black is preferable from the viewpoint of light shielding rate and image characteristics. Examples of carbon black include the following carbon blacks.
　三菱ケミカル社製：ＭＡ７、ＭＡ７７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ１００Ｒ、ＭＡ２２０、ＭＡ２３０、ＭＡ６００、＃５、＃１０、＃２０、＃２５、＃３０、＃３２、＃３３、＃４０、＃４４、＃４５、＃４７、＃５０、＃５２、＃５５、＃６５０、＃７５０、＃８５０、＃９５０、＃９６０、＃９７０、＃９８０、＃９９０、＃１０００、＃２２００、＃２３００、＃２３５０、＃２４００、＃２６００、＃３０５０、＃３１５０、＃３２５０、＃３６００、＃３７５０、＃３９５０、＃４０００、＃４０１０、ＯＩＬ７Ｂ、ＯＩＬ９Ｂ、ＯＩＬ１１Ｂ、ＯＩＬ３０Ｂ、ＯＩＬ３１Ｂ
　デグサ社製：Ｐｒｉｎｔｅｘ（登録商標。以下同じ。）３、Ｐｒｉｎｔｅｘ３ＯＰ、Ｐｒｉｎｔｅｘ３０、Ｐｒｉｎｔｅｘ３０ＯＰ、Ｐｒｉｎｔｅｘ４０、Ｐｒｉｎｔｅｘ４５、Ｐｒｉｎｔｅｘ５５、Ｐｒｉｎｔｅｘ６０、Ｐｒｉｎｔｅｘ７５、Ｐｒｉｎｔｅｘ８０、Ｐｒｉｎｔｅｘ８５、Ｐｒｉｎｔｅｘ９０、Ｐｒｉｎｔｅｘ　Ａ、Ｐｒｉｎｔｅｘ　Ｌ、Ｐｒｉｎｔｅｘ　Ｇ、Ｐｒｉｎｔｅｘ　Ｐ、Ｐｒｉｎｔｅｘ　Ｕ、Ｐｒｉｎｔｅｘ　Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２Ｖ、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ１８、Ｃｏｌｏｒ　Ｂｌａｃｋ　ＦＷ２００、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１６０、Ｃｏｌｏｒ　Ｂｌａｃｋ　Ｓ１７０
　キャボット社製：Ｍｏｎａｒｃｈ（登録商標。以下同じ。）１２０、Ｍｏｎａｒｃｈ２８０、Ｍｏｎａｒｃｈ４６０、Ｍｏｎａｒｃｈ８００、Ｍｏｎａｒｃｈ８８０、Ｍｏｎａｒｃｈ９００、Ｍｏｎａｒｃｈ１０００、Ｍｏｎａｒｃｈ１１００、Ｍｏｎａｒｃｈ１３００、Ｍｏｎａｒｃｈ１４００、Ｍｏｎａｒｃｈ４６３０、ＲＥＧＡＬ（登録商標。以下同じ。）９９、ＲＥＧＡＬ９９Ｒ、ＲＥＧＡＬ４１５、ＲＥＧＡＬ４１５Ｒ、ＲＥＧＡＬ２５０、ＲＥＧＡＬ２５０Ｒ、ＲＥＧＡＬ３３０、ＲＥＧＡＬ４００Ｒ、ＲＥＧＡＬ５５Ｒ０、ＲＥＧＡＬ６６０Ｒ、ＢＬＡＣＫ　ＰＥＡＲＬＳ４８０、ＰＥＡＲＬＳ１３０、ＶＵＬＣＡＮ（登録商標）　ＸＣ７２Ｒ、ＥＬＦＴＥＸ（登録商標）－８
　ビルラー社製：ＲＡＶＥＮ１１、ＲＡＶＥＮ１４、ＲＡＶＥＮ１５、ＲＡＶＥＮ１６、ＲＡＶＥＮ２２ＲＡＶＥＮ３０、ＲＡＶＥＮ３５、ＲＡＶＥＮ４０、ＲＡＶＥＮ４１０、ＲＡＶＥＮ４２０、ＲＡＶＥＮ４５０、ＲＡＶＥＮ５００、ＲＡＶＥＮ７８０、ＲＡＶＥＮ８５０、ＲＡＶＥＮ８９０Ｈ、ＲＡＶＥＮ１０００、ＲＡＶＥＮ１０２０、ＲＡＶＥＮ１０４０、ＲＡＶＥＮ１０６０Ｕ、ＲＡＶＥＮ１０８０Ｕ、ＲＡＶＥＮ１１７０、ＲＡＶＥＮ１１９０Ｕ、ＲＡＶＥＮ１２５０、ＲＡＶＥＮ１５００、ＲＡＶＥＮ２０００、ＲＡＶＥＮ２５００Ｕ、ＲＡＶＥＮ３５００、ＲＡＶＥＮ５０００、ＲＡＶＥＮ５２５０、ＲＡＶＥＮ５７５０、ＲＡＶＥＮ７０００ Made by Mitsubishi Chemical Corporation: MA7, MA77, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350 , # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Made by Degusa: Printex (registered trademark; the same applies hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexA. Ｕ、Ｐｒｉｎｔｅｘ Ｖ、ＰｒｉｎｔｅｘＧ、ＳｐｅｃｉａｌＢｌａｃｋ５５０、ＳｐｅｃｉａｌＢｌａｃｋ３５０、ＳｐｅｃｉａｌＢｌａｃｋ２５０、ＳｐｅｃｉａｌＢｌａｃｋ１００、ＳｐｅｃｉａｌＢｌａｃｋ６、ＳｐｅｃｉａｌＢｌａｃｋ５、ＳｐｅｃｉａｌＢｌａｃｋ４、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２Ｖ、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ１８、Ｃｏｌｏｒ Ｂｌａｃｋ ＦＷ２００、Ｃｏｌｏｒ Ｂｌａｃｋ Ｓ１６０、Ｃｏｌｏｒ Black S170
Manufactured by Cabot Corporation: Monarch (registered trademark; the same applies hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark. REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN® XC72R, ELFTEX®-8
Made by Biller: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN10URA RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
　他の黒色顔料の例としては、チタンブラック、アニリンブラック、酸化鉄系黒色顔料、及び、赤色、緑色、青色の三色の有機顔料を混合して黒色顔料として用いることができる。 As an example of other black pigments, titanium black, aniline black, iron oxide-based black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.
　顔料として、例えば、硫酸バリウム、硫酸鉛、酸化チタン、黄色鉛、ベンガラ、酸化クロムを用いることもできる。これら各種の顔料は、複数種を併用することもできる。例えば、色度の調整のために、緑色顔料と黄色顔料とを併用したり、青色顔料と紫色顔料とを併用したりすることができる。 As the pigment, for example, barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, and chromium oxide can be used. A plurality of these various pigments can be used in combination. For example, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination for adjusting the chromaticity.
　顔料の平均粒径としては、カラーフィルターの着色層とした場合に、所望の発色が可能なものであればよく、特に限定されず、用いる顔料の種類によっても異なるが、１０～１００ｎｍの範囲内であることが好ましく、１０～７０ｎｍの範囲内であることがより好ましい。顔料の平均粒径が上記範囲であることにより、本発明における感光性樹脂組成物を用いて製造された液晶表示装置の色特性を高品質なものとすることができる傾向がある。
　カーボンブラックの平均粒径は、６０ｎｍ以下が好ましく、５０ｎｍ以下がさらに好ましく、また、２０ｎｍ以上が好ましく、例えば、２０～５０ｎｍが好ましく、２０～６０ｎｍがより好ましい。平均粒径を前記上限値以下とすることで、散乱が小さくなり、遮光性やコントラストなどの色特性の低下を抑制できる傾向がある。また、平均粒径を前記下限値以上とすることで、分散剤の量が過度に多くならずに済み、分散性が良好となる傾向がある。
　なお、カーボンブラックを含む上記顔料の平均粒径は、電子顕微鏡写真から一次粒子の大きさを直接計測する方法で求めることができる。具体的には、個々の一次粒子の短軸径と長軸径を計測し、その平均をその粒子の粒径とする。次に、１００個以上の粒子について、それぞれの粒子の体積（質量）を、求めた粒径の直方体と近似して求め、体積平均粒径を求めそれを平均粒径とする。なお、透過型電子顕微鏡（ＴＥＭ）または走査型電子顕微鏡（ＳＥＭ）のいずれを用いても同じ結果を得ることができる。 The average particle size of the pigment may be any as long as it can develop a desired color when it is used as a colored layer of a color filter, and is not particularly limited and varies depending on the type of pigment used, but is within the range of 10 to 100 nm. It is preferably in the range of 10 to 70 nm, and more preferably in the range of 10 to 70 nm. When the average particle size of the pigment is in the above range, the color characteristics of the liquid crystal display device manufactured by using the photosensitive resin composition of the present invention tend to be high quality.
The average particle size of carbon black is preferably 60 nm or less, more preferably 50 nm or less, more preferably 20 nm or more, for example, preferably 20 to 50 nm, and even more preferably 20 to 60 nm. By setting the average particle size to the upper limit or less, the scattering becomes small, and there is a tendency that deterioration of color characteristics such as light-shielding property and contrast can be suppressed. Further, by setting the average particle size to the lower limit value or more, the amount of the dispersant does not need to be excessively large, and the dispersibility tends to be good.
The average particle size of the pigment containing carbon black can be obtained by a method of directly measuring the size of the primary particles from an electron micrograph. Specifically, the minor axis diameter and the major axis diameter of each primary particle are measured, and the average thereof is taken as the particle size of the particle. Next, for 100 or more particles, the volume (mass) of each particle is obtained by approximating it to a rectangular parallelepiped having the obtained particle size, and the volume average particle size is obtained and used as the average particle size. The same result can be obtained by using either a transmission electron microscope (TEM) or a scanning electron microscope (SEM).
　本発明における感光性樹脂組成物が（Ｄ）色材を含有する場合、色材として少なくとも顔料を含むことが好ましいが、その他に、本発明の効果に影響を及ぼさない範囲で染料を併用してもよい。併用できる染料としては、例えば、アゾ系染料、アントラキノン系染料、フタロシアニン系染料、キノンイミン系染料、キノリン系染料、ニトロ系染料、カルボニル系染料、メチン系染料が挙げられる。 When the photosensitive resin composition in the present invention contains (D) a coloring material, it is preferable that the photosensitive resin composition contains at least a pigment as the coloring material, but in addition, a dye is used in combination as long as it does not affect the effect of the present invention. May be good. Examples of dyes that can be used in combination include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
　アゾ系染料としては、例えば、Ｃ．Ｉ．アシッドイエロー１１、Ｃ．Ｉ．アシッドオレンジ７、Ｃ．Ｉ．アシッドレッド３７、Ｃ．Ｉ．アシッドレッド１８０、Ｃ．Ｉ．アシッドブルー２９、Ｃ．Ｉ．ダイレクトレッド２８、Ｃ．Ｉ．ダイレクトレッド８３、Ｃ．Ｉ．ダイレクトイエロー１２、Ｃ．Ｉ．ダイレクトオレンジ２６、Ｃ．Ｉ．ダイレクトグリーン２８、Ｃ．Ｉ．ダイレクトグリーン５９、Ｃ．Ｉ．リアクティブイエロー２、Ｃ．Ｉ．リアクティブレッド１７、Ｃ．Ｉ．リアクティブレッド１２０、Ｃ．Ｉ．リアクティブブラック５、Ｃ．Ｉ．ディスパースオレンジ５、Ｃ．Ｉ．ディスパースレッド５８、Ｃ．Ｉ．ディスパースブルー１６５、Ｃ．Ｉ．ベーシックブルー４１、Ｃ．Ｉ．ベーシックレッド１８、Ｃ．Ｉ．モルダントレッド７、Ｃ．Ｉ．モルダントイエロー５、Ｃ．Ｉ．モルダントブラック７が挙げられる。 Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Moldant Black 7 can be mentioned.
　アントラキノン系染料としては、例えば、Ｃ．Ｉ．バットブルー４、Ｃ．Ｉ．アシッドブルー４０、Ｃ．Ｉ．アシッドグリーン２５、Ｃ．Ｉ．リアクティブブルー１９、Ｃ．Ｉ．リアクティブブルー４９、Ｃ．Ｉ．ディスパースレッド６０、Ｃ．Ｉ．ディスパースブルー５６、Ｃ．Ｉ．ディスパースブルー６０が挙げられる。
　この他、フタロシアニン系染料として、例えば、Ｃ．Ｉ．パッドブルー５等が、キノンイミン系染料として、例えば、Ｃ．Ｉ．ベーシックブルー３、Ｃ．Ｉ．ベーシックブルー９等が、キノリン系染料として、例えば、Ｃ．Ｉ．ソルベントイエロー３３、Ｃ．Ｉ．アシッドイエロー３、Ｃ．Ｉ．ディスパースイエロー６４等が、ニトロ系染料として、例えば、Ｃ．Ｉ．アシッドイエロー１、Ｃ．Ｉ．アシッドオレンジ３、Ｃ．Ｉ．ディスパースイエロー４２が挙げられる。 Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 can be mentioned.
In addition, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like can be used as quinoneimine dyes, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are used as quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 can be mentioned.
　本発明における感光性樹脂組成物が（Ｄ）色材を含有する場合、（Ｄ）色材の含有割合は、感光性樹脂組成物中の全固形分に対して通常１～７０質量％の範囲で選ぶことができる。この範囲の中では、２０質量％以上がより好ましく、３０質量％以上がさらに好ましく、４０質量％以上が特に好ましく、また、６０質量％以下がより好ましい。
　上記の上限及び下限は任意に組み合わせることができる。例えば、１～７０質量％が好ましく、２０～７０質量％がより好ましく、３０～６０質量％がさらに好ましく、４０～６０質量％が特に好ましい。 When the photosensitive resin composition in the present invention contains (D) a coloring material, the content ratio of the (D) coloring material is usually in the range of 1 to 70% by mass with respect to the total solid content in the photosensitive resin composition. You can choose with. Within this range, 20% by mass or more is more preferable, 30% by mass or more is further preferable, 40% by mass or more is particularly preferable, and 60% by mass or less is more preferable.
The above upper and lower limits can be combined arbitrarily. For example, 1 to 70% by mass is preferable, 20 to 70% by mass is more preferable, 30 to 60% by mass is further preferable, and 40 to 60% by mass is particularly preferable.
　本発明における感光性樹脂組成物は、後述するように種々な用途に使用することができるが、優れた画像形成性は、カラーフィルター用ブラックマトリックスの形成に使用した場合に、特に効果的である。ブラックマトリックス形成に使用する場合には（Ｄ）色材として、前述したカーボンブラックやチタンブラック等の黒色色材を使用するか、黒色以外の色材を複数種類混合し黒色に調整して使用すればよい。その中でも分散安定性及び遮光性の観点から、カーボンブラックを使用することが、特に好ましい。 The photosensitive resin composition in the present invention can be used for various purposes as described later, but excellent image forming property is particularly effective when used for forming a black matrix for a color filter. .. When used to form a black matrix, (D) use a black color material such as carbon black or titanium black described above, or mix multiple types of color materials other than black and adjust to black. Just do it. Among them, it is particularly preferable to use carbon black from the viewpoint of dispersion stability and light-shielding property.
　本発明における感光性樹脂組成物は、ブラックマトリックス形成に使用する場合、遮光度を上げるために黒色色材濃度を多くする必要がある。この観点から、黒色色材の含有割合は感光性樹脂組成物の全固形分に対し４０質量％以上であり、４５質量％以上が好ましく、５０質量％以上がより好ましい。また、画像形成性能の観点からは、７０質量％以下が好ましく、６５質量％以下がより好ましい。
　上記上限及び下限は任意に組み合わせることができる。例えば、４０～７０質量％が好ましく、４５～７０質量％がより好ましく、５０～６５質量％がさらに好ましい。 When the photosensitive resin composition in the present invention is used for forming a black matrix, it is necessary to increase the concentration of the black colorant in order to increase the degree of light shielding. From this viewpoint, the content ratio of the black color material is 40% by mass or more, preferably 45% by mass or more, and more preferably 50% by mass or more with respect to the total solid content of the photosensitive resin composition. Further, from the viewpoint of image forming performance, 70% by mass or less is preferable, and 65% by mass or less is more preferable.
The above upper limit and lower limit can be arbitrarily combined. For example, 40 to 70% by mass is preferable, 45 to 70% by mass is more preferable, and 50 to 65% by mass is further preferable.
　本発明における感光性樹脂組成物が（Ｄ）色材を含有する場合、（Ｄ）色材の含有割合は、（Ａ）アルカリ可溶性樹脂１００質量部あたり、通常２０質量部以上、好ましくは３０質量部以上、より好ましくは４０質量部以上、さらに好ましくは６０質量部以上、よりさらに好ましくは８０質量部以上、特に好ましくは１２０質量部以上、最も好ましくは１６０質量部以上であり、また通常５００質量部以下、好ましくは３００質量部以下、より好ましくは２８０質量部以下である。（Ｄ）色材の含有割合を前記下限値以上とすることで未露光部の現像液に対する溶解性の低下を抑制しやすい傾向がある。また、前記上限値以下とすることで所望の画像膜厚が得やすい傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、２０～５００質量部が好ましく、３０～５００質量部がより好ましく、４０～５００質量部がさらに好ましく、６０～３００質量部がよりさらに好ましく、８０～３００質量部がことさら好ましく、１２０～２８０質量部が特に好ましく、１６０～２８０質量部が最も好ましい。 When the photosensitive resin composition in the present invention contains (D) a coloring material, the content ratio of the (D) coloring material is usually 20 parts by mass or more, preferably 30 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. More than parts, more preferably 40 parts by mass or more, still more preferably 60 parts by mass or more, still more preferably 80 parts by mass or more, particularly preferably 120 parts by mass or more, most preferably 160 parts by mass or more, and usually 500 parts by mass. Parts or less, preferably 300 parts by mass or less, more preferably 280 parts by mass or less. (D) By setting the content ratio of the coloring material to the lower limit value or more, it tends to be easy to suppress the decrease in the solubility of the unexposed portion in the developing solution. Further, when the value is not more than the upper limit, it tends to be easy to obtain a desired image film thickness.
The above upper and lower limits can be combined arbitrarily. For example, 20 to 500 parts by mass is preferable, 30 to 500 parts by mass is more preferable, 40 to 500 parts by mass is further preferable, 60 to 300 parts by mass is more preferable, 80 to 300 parts by mass is particularly preferable, and 120 to 280 parts is particularly preferable. The parts by mass are particularly preferable, and 160 to 280 parts by mass are most preferable.
＜分散剤＞
　本発明における感光性組成物が（Ｄ）色材を含有する場合、色材を微細に分散させ、且つその分散状態を安定化させることが品質の安定性確保には重要なため、さらに分散剤を含むことが好ましい。
　分散剤としては、官能基を有する高分子分散剤が好ましく、さらには、分散安定性の面からカルボキシ基；リン酸基；スルホン酸基；又はこれらの塩基；一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の官能基を有する高分子分散剤が好ましい。中でも特に、一級、二級又は三級アミノ基；四級アンモニウム塩基；ピリジン、ピリミジン、ピラジン等の含窒素ヘテロ環由来の基、等の塩基性官能基を有する高分子分散剤が特に好ましい。これら塩基性官能基を有する高分子分散剤を使用することにより、分散性を良好にできる傾向がある。 <Dispersant>
When the photosensitive composition in the present invention contains (D) a coloring material, it is important to finely disperse the coloring material and stabilize the dispersed state thereof in order to ensure quality stability. It is preferable to include.
As the dispersant, a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxy group; a phosphate group; a sulfonic acid group; or these groups; a primary, secondary or tertiary amino group. A quaternary ammonium base; a polymer dispersant having a functional group such as a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine is preferable. Among them, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine is particularly preferable. By using a polymer dispersant having these basic functional groups, the dispersibility tends to be good.
　高分子分散剤としては、例えばウレタン系分散剤、アクリル系分散剤、ポリエチレンイミン系分散剤、ポリアリルアミン系分散剤、アミノ基を持つモノマーとマクロモノマーからなる分散剤、ポリオキシエチレンアルキルエーテル系分散剤、ポリオキシエチレンジエステル系分散剤、ポリエーテルリン酸系分散剤、ポリエステルリン酸系分散剤、ソルビタン脂肪族エステル系分散剤、脂肪族変性ポリエステル系分散剤を挙げることができる。 Examples of the polymer dispersant include urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ether-based dispersions. Examples thereof include agents, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
　このような分散剤の具体例としては、商品名で、ＥＦＫＡ（登録商標。エフカーケミカルズビーブイ（ＥＦＫＡ）社製。）、Ｄｉｓｐｅｒｂｙｋ（登録商標。ビックケミー社製。）、ディスパロン（登録商標。楠本化成社製。）、ＳＯＬＳＰＥＲＳＥ（登録商標。ルーブリゾール社製。）、ＫＰ（信越化学工業社製）、ポリフロー又はフローレン（登録商標。共栄社化学社製。）、アジスパー（登録商標。味の素ファインテクノ社製。）を挙げることができる。
　これらの高分子分散剤は１種を単独で使用してもよく、又は２種以上を併用してもよい。 Specific examples of such a dispersant include EFKA (registered trademark, manufactured by EFKA), Disperbyk (registered trademark, manufactured by Big Chemie), and Disparon (registered trademark, manufactured by Kusumoto Kasei) under the trade names. SOLSPERSE (registered trademark, manufactured by Lubrizol), KP (made by Shinetsu Chemical Industry Co., Ltd.), Polyflow or Floren (registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.), Azisper (registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.) .) Can be mentioned.
These polymer dispersants may be used alone or in combination of two or more.
　これらの内、密着性及び直線性の面から、分散剤は塩基性官能基を有するウレタン系高分子分散剤及び／又はアクリル系高分子分散剤を含むことが好ましく、ウレタン系高分子分散剤を含むことが密着性の面でより好ましい。また、分散性、保存性の面から、塩基性官能基を有し、ポリエステル及び／又はポリエーテル結合を有する高分子分散剤が好ましい。 Among these, from the viewpoint of adhesion and linearity, the dispersant preferably contains a urethane-based polymer dispersant having a basic functional group and / or an acrylic polymer dispersant, and the urethane-based polymer dispersant is used. It is more preferable to include it in terms of adhesion. Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and having a polyester and / or a polyether bond is preferable.
　高分子分散剤の重量平均分子量（Ｍｗ）は通常７００以上、好ましくは１０００以上であり、また通常１０００００以下、好ましくは５００００以下であり、より好ましくは３００００以下である。前記上限値以下とすることで、顔料濃度が高い時でもアルカリ現像性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、７００～１０００００が好ましく、７００～５００００がより好ましく、１０００～３００００がさらに好ましい。
　ウレタン系及びアクリル系高分子分散剤としては、例えば、Ｄｉｓｐｅｒｂｙｋ１６０～１６７、１８２シリーズ（いずれもウレタン系）、Ｄｉｓｐｅｒｂｙｋ２０００，２００１（いずれもアクリル系）（以上すべてビックケミー社製）が挙げられる。上記の塩基性官能基を有し、ポリエステル及び／又はポリエーテル結合を有するウレタン系高分子分散剤で重量平均分子量３００００以下の特に好ましいものとしてＤｉｓｐｅｒｂｙｋ１６７、１８２が挙げられる。 The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less, and more preferably 30,000 or less. By setting the value to the upper limit or less, the alkali developability tends to be good even when the pigment concentration is high.
The above upper and lower limits can be combined arbitrarily. For example, 700 to 100,000 is preferable, 700 to 50,000 is more preferable, and 1,000 to 30,000 is even more preferable.
Examples of the urethane-based and acrylic polymer dispersants include Disperbyk 160 to 167, 182 series (all urethane-based) and Disperbyk2000, 2001 (all acrylic-based) (all manufactured by Big Chemie). Disperbyk 167 and 182 are particularly preferable urethane-based polymer dispersants having the above-mentioned basic functional groups and having polyester and / or polyether bonds and having a weight average molecular weight of 30,000 or less.
＜ウレタン系高分子分散剤＞
　ウレタン系高分子分散剤として好ましい化学構造を具体的に例示するならば、例えば、ポリイソシアネート化合物と、分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物と、同一分子内に活性水素と３級アミノ基を有する化合物とを反応させることによって得られる、重量平均分子量１０００～２０００００の分散樹脂が挙げられる。 <Urethane-based polymer dispersant>
Specific examples of a preferable chemical structure as a urethane-based polymer dispersant include a polyisocyanate compound and a compound having one or two hydroxyl groups in the molecule and having a number average molecular weight of 300 to 10,000 in the same molecule. Examples thereof include a dispersed resin having a weight average molecular weight of 1000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group.
　上記のポリイソシアネート化合物の例としては、パラフェニレンジイソシアネート、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、ナフタレン－１，５－ジイソシアネート、トリジンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンメチルエステルジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、ダイマー酸ジイソシアネート等の脂肪族ジイソシアネート、イソホロンジイソシアネート、４，４’－メチレンビス（シクロヘキシルイソシアネート）、ω，ω’－ジイソシネートジメチルシクロヘキサン等の脂環族ジイソシアネート、キシリレンジイソシアネート、α，α，α’，α’－テトラメチルキシリレンジイソシアネート等の芳香環を有する脂肪族ジイソシアネート、リジンエステルトリイソシアネート、１，６，１１－ウンデカントリイソシアネート、１，８－ジイソシアネート－４－イソシアネートメチルオクタン、１，３，６－ヘキサメチレントリイソシアネート、ビシクロヘプタントリイソシアネート、トリス（イソシアネートフェニルメタン）、トリス（イソシアネートフェニル）チオホスフェート等のトリイソシアネート、及びこれらの３量体、水付加物、及びこれらのポリオール付加物が挙げられる。ポリイソシアネートとして好ましいのは有機ジイソシアネートの三量体で、最も好ましいのはトリレンジイソシアネートの三量体とイソホロンジイソシアネートの三量体である。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, trizine diisocyanate and the like. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as dimerate diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), ω, ω Alicyclic diisocyanate such as'-diisocyanate dimethylcyclohexane, aliphatic diisocyanate having aromatic ring such as xylylene diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1, 6,11-Undecantriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptantriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate Such as triisocyanates, trimerics thereof, water adducts, and polyol adducts thereof. The polyisocyanate is preferably a trimer of organic diisocyanate, and most preferably a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.
　イソシアネートの三量体の製造方法としては、前記ポリイソシアネート類を適当な三量化触媒、例えば、第３級アミン類、ホスフィン類、アルコキシド類、金属酸化物、カルボン酸塩類等を用いてイソシアネート基の部分的な三量化を行い、触媒毒の添加により三量化を停止させた後、未反応のポリイソシアネートを溶剤抽出、薄膜蒸留により除去して目的のイソシアヌレート基含有ポリイソシアネートを得る方法が挙げられる。 As a method for producing an isocyanate trimer, the polyisocyanate is subjected to an isocyanate group using an appropriate trimerization catalyst, for example, a tertiary amine, a phosphine, an alkoxide, a metal oxide, a carboxylate, or the like. A method of partially trimerizing, stopping the trimerization by adding a catalytic poison, and then removing the unreacted polyisocyanate by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate can be mentioned. ..
　同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物としては、ポリエーテルグリコール、ポリエステルグリコール、ポリカーボネートグリコール、ポリオレフィングリコール等、及びこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化されたもの及びこれら２種類以上の混合物が挙げられる。 As a compound having one or two hydroxyl groups in the same molecule and having an average molecular weight of 300 to 10,000, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one-terminal hydroxyl group of these compounds have 1 to 1 carbon atoms. Examples thereof include those analkylated with 25 alkyl groups and mixtures of two or more of these.
　ポリエーテルグリコールとしては、ポリエーテルジオール、ポリエーテルエステルジオール、及びこれら２種類以上の混合物が挙げられる。ポリエーテルジオールとしては、アルキレンオキシドを単独又は共重合させて得られるもの、例えばポリエチレングリコール、ポリプロピレングリコール、ポリエチレン－プロピレングリコール、ポリオキシテトラメチレングリコール、ポリオキシヘキサメチレングリコール、ポリオキシオクタメチレングリコール及びそれらの２種以上の混合物が挙げられる。 Examples of the polyether glycol include a polyether diol, a polyether ester diol, and a mixture of two or more of these. Examples of the polyether diol include those obtained by using alkylene oxide alone or in copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and them. A mixture of two or more of the above can be mentioned.
　ポリエーテルエステルジオールとしては、エーテル基含有ジオールもしくは他のグリコールとの混合物をジカルボン酸又はそれらの無水物と反応させるか、又はポリエステルグリコールにアルキレンオキシドを反応させることによって得られるもの、例えばポリ（ポリオキシテトラメチレン）アジペートが挙げられる。ポリエーテルグリコールとして最も好ましいのはポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール又はこれらの化合物の片末端水酸基が炭素数１～２５のアルキル基でアルコキシ化された化合物である。 Polyester ester diols are obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly). Oxytetramethylene) adipate can be mentioned. The most preferable polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.
　ポリエステルグリコールとしては、例えば、ジカルボン酸（コハク酸、グルタル酸、アジピン酸、セバシン酸、フマル酸、マレイン酸、フタル酸等）又はそれらの無水物とグリコール（エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２－プロピル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、２－メチル－２，４－ペンタンジオール、２，２，４－トリメチル－１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２，５－ジメチル－２，５－ヘキサンジオール、１，８－オクタメチレングリコール、２－メチル－１，８－オクタメチレングリコール、１，９－ノナンジオール等の脂肪族グリコール、ビスヒドロキシメチルシクロヘキサン等の脂環族グリコール、キシリレングリコール、ビスヒドロキシエトキシベンゼン等の芳香族グリコール、Ｎ－メチルジエタノールアミン等のＮ－アルキルジアルカノールアミン等）とを重縮合させて得られたもの、例えばポリエチレンアジペート、ポリブチレンアジペート、ポリヘキサメチレンアジペート、ポリエチレン／プロピレンアジペート等、又は前記ジオール類又は炭素数１～２５の１価アルコールを開始剤として用いて得られるポリラクトンジオール又はポリラクトンモノオール、例えばポリカプロラクトングリコール、ポリメチルバレロラクトン及びこれらの２種以上の混合物が挙げられる。ポリエステルグリコールとして最も好ましいのはポリカプロラクトングリコール又は炭素数１～２５のアルコールを開始剤としたポリカプロラクトンである。 Examples of polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene). Glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neo Pentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol , 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl Alicyclic glycols such as -2,5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, 1,9-nonanediol, and alicyclic glycols such as bishydroxymethylcyclohexane. , Xylylene glycol, aromatic glycols such as bishydroxyethoxybenzene, N-alkyldialkanolamines such as N-methyldiethanolamine, etc.) and obtained by polycondensation, for example, polyethylene adipate, polybutylene adipate, polyhexa. Polylactone diols or polylactone monools obtained by using methylene adipate, polyethylene / propylene adipate, etc., or the above diols or monovalent alcohols having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone glycol, polymethylvalerolactone and Examples thereof include a mixture of two or more of these. The most preferable polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.
　ポリカーボネートグリコールとしては、例えば、ポリ（１，６－ヘキシレン）カーボネート、ポリ（３－メチル－１，５－ペンチレン）カーボネート、ポリオレフィングリコールとしてはポリブタジエングリコール、水素添加型ポリブタジエングリコール、水素添加型ポリイソプレングリコールが挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Can be mentioned.
These may be used alone or in combination of two or more.
　同一分子内に水酸基を１個又は２個有する化合物の数平均分子量は、通常３００～１００００、好ましくは５００～６０００、より好ましくは１０００～４０００である。
　次いで、同一分子内に活性水素と３級アミノ基を有する化合物について説明する。活性水素、即ち、酸素原子、窒素原子又はイオウ原子に直接結合している水素原子としては、水酸基、アミノ基、チオール基等の官能基中の水素原子が挙げられ、中でもアミノ基、特に１級のアミノ基の水素原子が好ましい。 The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.
Next, a compound having an active hydrogen and a tertiary amino group in the same molecule will be described. Examples of active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, include a hydrogen atom in a functional group such as a hydroxyl group, an amino group and a thiol group, and among them, an amino group, particularly a first-class one. The hydrogen atom of the amino group of is preferable.
　３級アミノ基は、特に限定されないが、例えば炭素数１～４のアルキル基を有するアミノ基、又はヘテロ環構造、より具体的にはイミダゾール環又はトリアゾール環、などが挙げられる。
　このような同一分子内に活性水素と３級アミノ基を有する化合物を例示するならば、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジプロピル－１，３－プロパンジアミン、Ｎ，Ｎ－ジブチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジプロピルエチレンジアミン、Ｎ，Ｎ－ジブチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジプロピル－１，４－ブタンジアミン、Ｎ，Ｎ－ジブチル－１，４－ブタンジアミンが挙げられる。 The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, and more specifically, an imidazole ring or a triazole ring.
To exemplify such a compound having an active hydrogen and a tertiary amino group in the same molecule, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-Butanediamine.
　３級アミノ基が含窒素ヘテロ環構造である場合の含窒素ヘテロ環としては、例えば、ピラゾール環、イミダゾール環、トリアゾール環、テトラゾール環、インドール環、カルバゾール環、インダゾール環、ベンズイミダゾール環、ベンゾトリアゾール環、ベンゾオキサゾール環、ベンゾチアゾール環、ベンゾチアジアゾール環等のＮ含有ヘテロ５員環、ピリジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、アクリジン環、イソキノリン環等の含窒素ヘテロ６員環が挙げられる。これらの含窒素ヘテロ環のうち、イミダゾール環又はトリアゾール環が好ましい。 Examples of the nitrogen-containing heterocycle when the tertiary amino group has a nitrogen-containing heterocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indol ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzotriazole. N-containing hetero 5-membered ring such as ring, benzoxazole ring, benzothiazole ring, benzothiazol ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, aclysine ring, isoquinoline ring and other nitrogen-containing hetero 6-membered rings. Can be mentioned. Of these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferable.
　これらのイミダゾール環とアミノ基を有する化合物を具体的に例示するならば、１－（３－アミノプロピル）イミダゾール、ヒスチジン、２－アミノイミダゾール、１－（２－アミノエチル）イミダゾールが挙げられる。また、トリアゾール環とアミノ基を有する化合物を具体的に例示するならば、３－アミノ－１，２，４－トリアゾール、５－（２－アミノ－５－クロロフェニル）－３－フェニル－１Ｈ－１，２，４－トリアゾール、４－アミノ－４Ｈ－１，２，４－トリアゾール－３，５－ジオール、３－アミノ－５－フェニル－１Ｈ－１，３，４－トリアゾール、５－アミノ－１，４－ジフェニル－１，２，３－トリアゾール、３－アミノ－１－ベンジル－１Ｈ－２，４－トリアゾールが挙げられる。中でも、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、１－（３－アミノプロピル）イミダゾール、３－アミノ－１，２，４－トリアゾールが好ましい。 Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, and 1- (2-aminoethyl) imidazole. Specific examples of the compound having a triazole ring and an amino group include 3-amino-1,2,4-triazole and 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1. , 2,4-Triazole, 4-amino-4H-1,2,4-Triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-Diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。
　ウレタン系高分子分散剤を製造する際の原料の好ましい配合比率はポリイソシアネート化合物１００質量部に対し、同一分子内に水酸基を１個又は２個有する数平均分子量３００～１００００の化合物が１０～２００質量部、好ましくは２０～１９０質量部、さらに好ましくは３０～１８０質量部、同一分子内に活性水素と３級アミノ基を有する化合物が０．２～２５質量部、好ましくは０．３～２４質量部である。 These may be used alone or in combination of two or more.
The preferable blending ratio of the raw material for producing a urethane-based polymer dispersant is 10 to 200 for a compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 with respect to 100 parts by mass of the polyisocyanate compound. By mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass of the compound having an active hydrogen and a tertiary amino group in the same molecule. It is a mass part.
　ウレタン系高分子分散剤の製造はポリウレタン樹脂製造に係る公知の方法に従って行われる。製造する際に用いる溶媒としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロペンタノン、シクロヘキサノン、イソホロン等のケトン類、酢酸エチル、酢酸ブチル、酢酸セロソルブ等のエステル類、ベンゼン、トルエン、キシレン、ヘキサン等の炭化水素類、ダイアセトンアルコール、イソプロパノール、第二ブタノール、第三ブタノール等一部のアルコール類、塩化メチレン、クロロホルム等の塩化物、テトラヒドロフラン、ジエチルエーテル等のエーテル類、ジメチルホルムアミド、Ｎ－メチルピロリドン、ジメチルスルホキサイド等の非プロトン性極性溶媒が用いられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 The urethane-based polymer dispersant is produced according to a known method for producing a polyurethane resin. Examples of the solvent used in the production include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve acetate, benzene, toluene and xylene. Hydrocarbons such as hexane, diacetone alcohol, isopropanol, second butanol, some alcohols such as tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N- Aprotonic polar solvents such as methylpyrrolidone and dimethylsulfoxide are used. These may be used alone or in combination of two or more.
　上記製造に際して、通常、ウレタン化反応触媒が用いられる。この触媒としては、例えば、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジオクトエート、スタナスオクトエート等の錫系、鉄アセチルアセトナート、塩化第二鉄等の鉄系、トリエチルアミン、トリエチレンジアミン等の３級アミン系の１種又は２種以上が挙げられる。 In the above production, a urethanization reaction catalyst is usually used. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stanas octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. One type or two or more types of primary amine type can be mentioned.
＜アミン価の測定方法＞
　分散剤の３級アミン価は、分散剤試料中の溶媒を除いた固形分１ｇあたりの塩基量と当量のＫＯＨの質量で表し、次の方法により測定することができる。
　１００ｍＬのビーカーに分散剤試料の０．５～１．５ｇを精秤し、５０ｍＬの酢酸で溶解する。ｐＨ電極を備えた自動滴定装置を使って、この溶液を０．１ｍｏｌ／ＬのＨＣｌＯ4（過塩素酸）酢酸溶液にて中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点とし次式によりアミン価を求める。 <Measuring method of amine value>
The tertiary amine value of the dispersant is expressed by the amount of base per 1 g of solid content excluding the solvent in the dispersant sample and the equivalent amount of KOH, and can be measured by the following method.
Weigh 0.5-1.5 g of the dispersant sample into a 100 mL beaker and dissolve in 50 mL of acetic acid. This solution is neutralized and titrated with 0.1 mol / L HClO 4 (perchloric acid) acetic acid solution using an automatic titrator equipped with a pH electrode. The amine value is calculated by the following formula with the inflection point of the titration pH curve as the titration end point.
　アミン価［ｍｇＫＯＨ／ｇ］＝（５６１×Ｖ）／（Ｗ×Ｓ）
〔但し、Ｗ：分散剤試料秤取量［ｇ］、Ｖ：滴定終点での滴定量［ｍＬ］、Ｓ：分散剤試料の固形分濃度［質量％］を表す。〕
　同一分子内に活性水素と３級アミノ基を有する化合物の導入量は反応後のアミン価で１～１００ｍｇＫＯＨ／ｇの範囲に制御するのが好ましい。より好ましくは５～９５ｍｇＫＯＨ／ｇの範囲である。アミン価は、塩基性アミノ基を酸により中和滴定し、酸価に対応させてＫＯＨのｍｇ数で表した値である。アミン価を前記下限値以上とすることで分散性が良好となる傾向がある。また、前記上限値以下とすることで現像性が良好となる傾向がある。 Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Dispersant sample weighing amount [g], V: Titration determination at the end point of titration [mL], S: Solid content concentration [mass%] of the dispersant sample. ]
The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value expressed by the number of mg of KOH corresponding to the acid value by neutralizing and titrating the basic amino group with an acid. Dispersibility tends to be good when the amine value is at least the above lower limit value. Further, when the value is not more than the upper limit value, the developability tends to be good.
　以上の反応で高分子分散剤にイソシアネート基が残存する場合にはさらに、アルコールやアミノ化合物でイソシアネート基を消費すると生成物の経時安定性が高くなるので好ましい。
　ウレタン系高分子分散剤の重量平均分子量（Ｍｗ）は通常１０００～２０００００、好ましくは２０００～１０００００、より好ましくは３０００～５００００の範囲である。特に３００００以下が好ましい。前記下限値以上とすることで分散性及び分散安定性が良好となる傾向がある。また、前記上限値以下とすることで溶解性が良好となる傾向がある。上記の上限及び下限は任意に組み合わせることができる。例えば、１０００～３００００、２０００～３００００、３０００～３００００であってもよい。分子量が３００００以下であると、特に顔料濃度の高い場合でも、アルカリ現像性が良好となる傾向がある。このような特に好ましい市販のウレタン分散剤としては、例えば、Ｄｉｓｐｅｒｂｙｋ１６７、１８２（ビックケミー社）が挙げられる。 When the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to consume the isocyanate group with an alcohol or an amino compound because the stability of the product with time becomes high.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1000 to 200,000, preferably 2000 to 100,000, and more preferably 3000 to 50,000. Especially, 30,000 or less is preferable. When the value is equal to or higher than the lower limit, the dispersibility and dispersion stability tend to be good. Further, when the value is not more than the upper limit, the solubility tends to be good. The above upper and lower limits can be combined arbitrarily. For example, it may be 1000 to 30000, 2000 to 30000, 3000 to 30000. When the molecular weight is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is particularly high. Examples of such a particularly preferable commercially available urethane dispersant include Disperbyk 167 and 182 (Big Chemie).
　本発明における感光性樹脂組成物が分散剤を含有する場合、分散剤の含有割合は、感光性樹脂組成物の全固形分中、通常５０質量％以下、好ましくは３０質量％以下、より好ましくは２０質量％以下、通常１質量％以上、好ましくは３質量％以上、より好ましくは５質量％以上、さらに好ましくは７質量％以上、特に好ましくは１０質量％以上である。上記の上限及び下限は任意に組み合わせることができる。例えば、１～５０質量％が好ましく、３～５０質量％がより好ましく、５～３０質量％がさらに好ましく、７～３０質量％がよりさらに好ましく、１０～２０質量％が特に好ましい。
　また、分散剤の含有割合は、（Ｄ）色材１００質量部に対して、通常５質量部以上、好ましくは１０質量部以上で、より好ましくは１５質量部以上であり、通常２００質量部以下、好ましくは８０質量部以下、より好ましくは５０質量部以下である。上記の上限及び下限は任意に組み合わせることができる。例えば、５～２００質量部が好ましく、１０～８０質量部がより好ましく、１５～５０質量部がさらに好ましい。
　前記下限値以上とすることで十分な分散性を確保しやすい傾向がある。また、前記上限値以下とすることで他の成分の割合を減らすことなく、色濃度、感度、成膜性などを十分なものとしやすい傾向がある。 When the photosensitive resin composition in the present invention contains a dispersant, the content ratio of the dispersant is usually 50% by mass or less, preferably 30% by mass or less, more preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. It is 20% by mass or less, usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more. The above upper and lower limits can be combined arbitrarily. For example, 1 to 50% by mass is preferable, 3 to 50% by mass is more preferable, 5 to 30% by mass is further preferable, 7 to 30% by mass is further preferable, and 10 to 20% by mass is particularly preferable.
The content ratio of the dispersant is usually 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and usually 200 parts by mass or less with respect to 100 parts by mass of the (D) coloring material. It is preferably 80 parts by mass or less, more preferably 50 parts by mass or less. The above upper and lower limits can be combined arbitrarily. For example, 5 to 200 parts by mass is preferable, 10 to 80 parts by mass is more preferable, and 15 to 50 parts by mass is further preferable.
When the value is equal to or higher than the lower limit, it tends to be easy to secure sufficient dispersibility. Further, when the value is not more than the upper limit, the color density, sensitivity, film forming property and the like tend to be sufficient without reducing the ratio of other components.
＜チオール類＞
　本発明における感光性樹脂組成物は、高感度化、基板への密着性の向上のため、チオール類を含有することが好ましい。チオール類の種類としては、例えば、ヘキサンジチオール、デカンジチオール、１，４－ジメチルメルカプトベンゼン、ブタンジオールビスチオプロピオネート、ブタンジオールビスチオグリコレート、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ブタンジオールビスチオプロピオネート、トリメチロールプロパントリスチオプロピオネート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオプロピオネート、ペンタエリスリトールテトラキスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、エチレングリコールビス（３－メルカプトブチレート）、プロピレングリコールビス（３－メルカプトブチレート）（ＰＧＭＢ），ブタンジオールビス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン；（商品名；カレンズＭＴ　ＢＤ１、昭和電工（株）製）、ブタンジオールトリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）；（商品名；カレンズＭＴ　ＰＥ１、昭和電工（株）製）、ペンタエリスリトールトリス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトイソブチレート）、ブタンジオールビス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトイソブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）（ＴＰＭＢ）、トリメチロールプロパントリス（２－メルカプトイソブチレート）（ＴＰＭＩＢ）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン（商品名：カレンズＭＴ　ＮＲ１、昭和電工（株）製）が挙げられる。これらは種々のものが１種を単独で、あるいは２種以上を混合して使用できる。
　ＰＧＭＢ、ＴＰＭＢ、ＴＰＭＩＢ、カレンズＭＴ　ＢＤ１、カレンズＭＴ　ＰＥ１、カレンズＭＴ　ＮＲ１などの多官能チオールが好ましく、その中でもカレンズＭＴ　ＢＤ１、カレンズＭＴ　ＰＥ１、カレンズＭＴ　ＮＲ１がさらに好ましく、カレンズＭＴ　ＰＥ１が特に好ましい。 <Thiols>
The photosensitive resin composition in the present invention preferably contains thiols in order to increase the sensitivity and the adhesion to the substrate. Examples of thiols include hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and trimethylolpropane tristhio. Glycolate, Butanediol Bisthiopropionate, Trimethylolpropane Tristhiopropionate, Trimethylolpropane Tristhioglycolate, Pentaerythritol Tetrakissthiopropionate, Pentaerythritol Tetrakissthioglycolate, Trishydroxyethyl Tristhiopropio Nate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate) (PGMB), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutylyloxy) Butan; (trade name; Karenz MT BD1, manufactured by Showa Denko Co., Ltd.), butanediol trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate); (trade name; Karenz MT) PE1, manufactured by Showa Denko Co., Ltd., pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) 3-Mercaptoisobutyrate), trimethylolpropanetris (3-mercaptobutyrate) (TPMB), trimethylolpropanetris (2-mercaptoisobutyrate) (TPMIB), 1,3,5-tris (3-mercapto) Butyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (trade name: Karenz MT NR1, manufactured by Showa Denko Co., Ltd.) can be mentioned. Various of these can be used alone or in admixture of two or more.
Polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are preferable, and among them, Karenz MT BD1, Karenz MT PE1, and Karenz MT NR1 are more preferable, and Karenz MT PE1 is particularly preferable.
　チオール化合物を用いる場合、チオール化合物の含有割合は、本発明における感光性樹脂組成物の全固形分に対して、好ましくは０．１質量％以上、より好ましくは０．３質量％以上、さらに好ましくは０．５質量％以上であり、通常１０質量％以下、好ましくは５質量％以下である。前記下限値以上とすることで感度低下を抑制できる傾向がある。また、前記上限値以下とすることで保存安定性を良好なものとしやすい傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～１０質量％が好ましく、０．３～１０質量％がより好ましく、０．５～５質量％がさらに好ましい。 When a thiol compound is used, the content ratio of the thiol compound is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably, with respect to the total solid content of the photosensitive resin composition in the present invention. Is 0.5% by mass or more, usually 10% by mass or less, preferably 5% by mass or less. By setting the value to the lower limit or more, there is a tendency that the decrease in sensitivity can be suppressed. Further, when the value is not more than the upper limit, the storage stability tends to be improved.
The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.3 to 10% by mass is more preferable, and 0.5 to 5% by mass is further preferable.
＜溶媒＞
　本発明における感光性樹脂組成物は、通常、（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤、並びに必要に応じて使用される（Ｄ）色材を含む各種材料が、有機溶媒に溶解又は分散した状態で使用される。
　溶媒としては、本発明の製造方法で用いた有機溶媒、本発明のカルボキシ基含有樹脂含有液に含有される有機溶媒がそのまま用いられる場合がある。
　有機溶媒としては、沸点（圧力１０１３．２５［ｈＰａ］条件下。以下、沸点に関しては全て同様。）が１００～３００℃の範囲のものを選択するのが好ましい。より好ましくは１２０～２８０℃の沸点をもつ溶媒である。
　このような有機溶媒としては、例えば、次のようなものが挙げられる。 <Solvent>
The photosensitive resin composition in the present invention usually contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and (D) a coloring material used as necessary. Various materials are used in a state of being dissolved or dispersed in an organic solvent.
As the solvent, the organic solvent used in the production method of the present invention or the organic solvent contained in the carboxy group-containing resin-containing liquid of the present invention may be used as it is.
As the organic solvent, it is preferable to select a solvent having a boiling point (pressure 1013.25 [hPa] condition; hereinafter, the same applies to all boiling points) in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.
Examples of such an organic solvent include the following.
　エチ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エチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテルのようなグリコールモノアルキルエーテル類； Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Glycol monoalkyl ethers such as monoethyl ether, tripropylene glycol methyl ether;
　エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテルのようなグリコールジアルキルエーテル類；
　エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメ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、ジエチレングリコールモノ－ｎ－ブ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、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートのようなグリコールアルキルエーテルアセテート類； Glycoldialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, 3-methyl-3-methoxybutyl acetate;
　エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテートなどのグリコールジアセテート類；
　シクロヘキサノールアセテートなどのアルキルアセテート類；
　アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテルのようなエーテル類；
　アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノンのようなケトン類；
　エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコールのような１価又は多価アルコール類；
　ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカンのような脂肪族炭化水素類；
　シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシルのような脂環式炭化水素類； Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamil ether, ethylisobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methylhexyl ketone, methylnonyl ketone, methoxymethylpentanone. Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
　ベンゼン、トルエン、キシレン、クメンのような芳香族炭化水素類；
　アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトンのような鎖状又は環状エステル類；
　３－メトキシプロピオン酸、３－エトキシプロピオン酸のようなアルコキシカルボン酸類； Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Chain or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
　ブチルクロライド、アミルクロライドのようなハロゲン化炭化水素類；
　メトキシメチルペンタノンのようなエーテルケトン類；
　アセトニトリル、ベンゾニトリルのようなニトリル類；
　上記に該当する市販の溶媒としては、例えば、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１及びＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８　ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ（「セロソルブ」は登録商標。以下同じ。）、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）が挙げられる。 Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;
Examples of commercially available solvents corresponding to the above include mineral spirit, valsol # 2, apco # 18 solvent, apco thinner, and socal solvent No. 1 and No. 2. Solvento # 150, Shell TS28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark; the same shall apply hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglime (any of them). Also the product name).
　これらの有機溶媒は、単独で用いてもよく、２種以上を併用してもよい。
　フォトリソグラフィー法にてカラーフィルターの画素又はブラックマトリックスを形成する場合、有機溶媒としては沸点が１００～２５０℃の範囲のものを選択するのが好ましい。より好ましくは１２０～２３０℃の沸点を持つものである。
　上記有機溶媒のうち、塗布性、表面張力などのバランスが良く、組成物中の構成成分の溶解度が比較的高い点からは、グリコールアルキルエーテルアセテート類が好ましい。 These organic solvents may be used alone or in combination of two or more.
When forming the pixels of the color filter or the black matrix by the photolithography method, it is preferable to select an organic solvent having a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120 to 230 ° C.
Of the above organic solvents, glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of the constituent components in the composition is relatively high.
　グリコールアルキルエーテルアセテート類は、単独で使用してもよいが、他の有機溶媒を併用してもよい。併用してもよい他の有機溶媒として、特に好ましいのはグリコールモノアルキルエーテル類である。中でも、特に組成物中の構成成分の溶解性からプロピレングリコールモノメチルエーテルが好ましい。グリコールモノアルキルエーテル類は極性が高く、添加量が多すぎると色材が凝集しやすく、後に得られる感光性樹脂組成物の粘度が上がっていくなどの保存安定性が低下する傾向があるので、溶媒中のグリコールモノアルキルエーテル類の割合は５質量％～３０質量％が好ましく、５質量％～２０質量％がより好ましい。 Glycol alkyl ether acetates may be used alone or in combination with other organic solvents. Glycol monoalkyl ethers are particularly preferable as other organic solvents that may be used in combination. Of these, propylene glycol monomethyl ether is particularly preferable because of the solubility of the constituents in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the coloring material tends to aggregate, and the viscosity of the photosensitive resin composition obtained later tends to increase, and the storage stability tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, more preferably 5% by mass to 20% by mass.
　２００℃以上の沸点をもつ有機溶媒（以下「高沸点溶媒」と称す場合がある。）を併用することも好ましい。このような高沸点溶媒を併用することにより、感光性樹脂組成物は乾きにくくなるが、組成物中における色材の均一な分散状態が、急激な乾燥により破壊されることを防止する効果がある。すなわち、例えばスリットノズル先端における、色材などの析出・固化による異物欠陥の発生を防止する効果がある。このような効果が高い点から、上述の各種溶媒の中でも、特にジプロピレングリコールメチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、及びジエチレングリコールモノエチルエーテルアセテート、１，４－ブタンジオールジアセテート、１，３－ブチレングリコールジアセテート、トリアセチン、１，６－ヘキサンジオールジアセテートが好ましい。 It is also preferable to use an organic solvent having a boiling point of 200 ° C. or higher (hereinafter, may be referred to as "high boiling point solvent") in combination. By using such a high boiling point solvent in combination, the photosensitive resin composition becomes difficult to dry, but there is an effect of preventing the uniformly dispersed state of the coloring material in the composition from being destroyed by rapid drying. .. That is, for example, there is an effect of preventing the generation of foreign matter defects due to precipitation and solidification of coloring materials and the like at the tip of the slit nozzle. Among the various solvents mentioned above, dipropylene glycol methyl ether acetate, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1, 3-butylene glycol diacetate, triacetin and 1,6-hexanediol diacetate are preferred.
　有機溶媒中の高沸点溶媒の含有割合は、０質量％～５０質量％が好ましく、０．５質量％～４０質量％がより好ましく、１質量％～３０質量％が特に好ましい。前記下限値以上とすることで、例えばスリットノズル先端で色材などが析出・固化して異物欠陥を惹き起こすことを抑制できる傾向がある。また、前記上限値以下とすることで組成物の乾燥温度が遅くなってカラーフィルター製造工程における、減圧乾燥プロセスのタクト不良や、プリベークのピン跡といった問題の発生を抑制できる傾向がある。 The content ratio of the high boiling point solvent in the organic solvent is preferably 0% by mass to 50% by mass, more preferably 0.5% by mass to 40% by mass, and particularly preferably 1% by mass to 30% by mass. By setting the value to the lower limit or more, for example, it tends to be possible to prevent the coloring material or the like from precipitating and solidifying at the tip of the slit nozzle to cause foreign matter defects. Further, when the value is not more than the upper limit, the drying temperature of the composition becomes slower, and there is a tendency that problems such as tact defects in the vacuum drying process and pin marks of prebake can be suppressed in the color filter manufacturing process.
　本発明における感光性樹脂組成物において、有機溶媒の含有割合は特に限定されないが、塗布し易さや粘度安定性の観点から、感光性樹脂組成物中の全固形分が好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上、また、好ましくは４０質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、特に好ましくは２０質量％以下である。 In the photosensitive resin composition of the present invention, the content ratio of the organic solvent is not particularly limited, but from the viewpoint of ease of application and viscosity stability, the total solid content in the photosensitive resin composition is preferably 5% by mass or more. It is more preferably 8% by mass or more, further preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 20% by mass or less. ..
＜感光性樹脂組成物のその他の配合成分＞
　本発明における感光性樹脂組成物には、上述の成分の他、密着向上剤、塗布性向上剤、顔料誘導体、現像改良剤、紫外線吸収剤、酸化防止剤等を適宜配合することができる。 <Other ingredients of the photosensitive resin composition>
In addition to the above-mentioned components, the photosensitive resin composition in the present invention may appropriately contain an adhesion improver, a coatability improver, a pigment derivative, a development improver, an ultraviolet absorber, an antioxidant and the like.
＜密着向上剤＞
　基板との密着性を改善するため、密着向上剤を含有させてもよく、例えば、シランカップリング剤、チタンカップリング剤が挙げられるが、特にシランカップリング剤が好ましい。
　このようなシランカップリング剤としては、例えば、ＫＢＭ－４０２、ＫＢＭ－４０３、ＫＢＭ－５０２、ＫＢＭ－５１０３、ＫＢＥ－９００７、Ｘ－１２－１０４８、Ｘ－１２－１０５０（信越シリコーン社製）、Ｚ－６０４０、Ｚ－６０４３、Ｚ－６０６２（東レ・ダウコーニング社製）が挙げられる。なお、シランカップリング剤は、１種を用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。
　さらに、シランカップリング剤以外の密着向上剤を本発明における感光性樹脂組成物に含有させてもよく、例えば、リン酸系密着向上剤、その他の密着向上剤が挙げられる。 <Adhesion improver>
In order to improve the adhesion to the substrate, an adhesion improver may be contained, and examples thereof include a silane coupling agent and a titanium coupling agent, and a silane coupling agent is particularly preferable.
Examples of such a silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, and X-12-1050 (manufactured by Shinetsu Silicone Co., Ltd.). Examples thereof include Z-6040, Z-6043, and Z-6062 (manufactured by Toray Dow Corning). As the silane coupling agent, one type may be used, or two or more types may be used in combination in any combination and ratio.
Further, an adhesion improver other than the silane coupling agent may be contained in the photosensitive resin composition of the present invention, and examples thereof include a phosphoric acid-based adhesion improver and other adhesion improvers.
　リン酸系密着向上剤としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましく、中でも下記一般式（ｇ１）、（ｇ２）、（ｇ３）で表されるものが好ましい。 As the phosphoric acid-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and among them, those represented by the following general formulas (g1), (g2) and (g3) are preferable.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　上記一般式（ｇ１）、（ｇ２）、（ｇ３）において、Ｒ51は各々独立に水素原子又はメチル基を示し、ｌ及びｌ’は各々独立に１～１０の整数、ｍは各々独立に１、２又は３である。
　その他の密着向上剤としては、ＴＥＧＯ*Ａｄｄ　Ｂｏｎｄ　ＬＴＨ（Ｅｖｏｎｉｋ社製）などが上げられる。これらの燐酸基含有化合物やその他の密着剤も１種類を単独で用いても、２種以上を組み合わせて使用してもよい。 In the above general formulas (g1), (g2), and (g3), R 51 independently represents a hydrogen atom or a methyl group, l and l'are independently integers of 1 to 10, and m is independently 1. 2 or 3.
Examples of other adhesion improvers include TEGO * Add Bond LTH (manufactured by Evonik). These phosphoric acid group-containing compounds and other adhesives may be used alone or in combination of two or more.
　本発明における感光性樹脂組成物が密着向上剤を含有する場合、感光性樹脂組成物中の密着向上剤の含有割合は特に限定されないが、感光性樹脂組成物中の全固形分中０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、０．５質量％以上がさらに好ましく、また、５質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下がさらに好ましく、１．５質量％以下が特に好ましい。前記下限値以上とすることで密着力が向上する傾向がある。また、前記上限値以下とすることで現像性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～５質量％が好ましく、０．０１～３質量％がより好ましく、０．１～２質量％がさらに好ましく、０．５～１．５質量％が特に好ましい。 When the photosensitive resin composition in the present invention contains an adhesion improver, the content ratio of the adhesion improver in the photosensitive resin composition is not particularly limited, but 0.01 in the total solid content in the photosensitive resin composition. By mass or more is preferable, 0.1% by mass or more is more preferable, 0.5% by mass or more is further preferable, 5% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is further preferable. , 1.5% by mass or less is particularly preferable. When the value is equal to or higher than the lower limit, the adhesion tends to be improved. Further, when the value is not more than the upper limit value, the developability tends to be good.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 5% by mass is preferable, 0.01 to 3% by mass is more preferable, 0.1 to 2% by mass is further preferable, and 0.5 to 1.5% by mass is particularly preferable.
＜塗布性向上剤＞
　本発明における感光性樹脂組成物には、塗布性向上のため、塗布性向上剤として界面活性剤を含有させてもよい。界面活性剤としては、例えば、アニオン系、カチオン系、非イオン系および両性界面活性剤を用いることができる。中でも、諸特性に悪影響を及ぼす可能性が低い点で、非イオン系界面活性剤を用いるのが好ましく、中でもフッ素系またはシリコーン系の界面活性剤が塗布性の面で効果的である。 <Applicability improver>
The photosensitive resin composition in the present invention may contain a surfactant as a coatability improver in order to improve the coatability. As the surfactant, for example, anionic, cationic, nonionic and amphoteric surfactants can be used. Among them, it is preferable to use a nonionic surfactant because it is unlikely to adversely affect various properties, and among them, a fluorine-based or silicone-based surfactant is effective in terms of coatability.
　このような界面活性剤としては、例えば、ＴＳＦ４４６０（モメンティブ・パフォーマンス・マテリアルズ社製）、ＤＦＸ－１８（ネオス社製）、ＢＹＫ－３００、ＢＹＫ－３２５、ＢＹＫ－３３０（ビックケミー社製）、ＫＰ３４０（信越シリコーン社製）、Ｆ－４７０、Ｆ－４７５、Ｆ－４７８、Ｆ－５５４、Ｆ－５５９（ＤＩＣ社製）、ＳＨ７ＰＡ（東レ・ダウコーニング社製）、ＤＳ－４０１（ダイキン社製）、Ｌ－７７（日本ユニカー社製）およびＦＣ４４３０（３Ｍジャパン社製）が挙げられる。なお、界面活性剤は、１種を用いてもよく、２種以上を任意の組み合わせ及び比率で併用してもよい。
　本発明における感光性樹脂組成物が界面活性剤を含有する場合、感光性樹脂組成物中の界面活性剤の含有割合は特に限定されないが、感光性樹脂組成物中の全固形分中０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、また、１．０質量％以下が好ましく、０．７質量％以下がより好ましく、０．５質量％以下がさらに好ましく、０．３質量％以下が特に好ましい。前記下限値以上とすることでレジスト塗布均一性がよくなる傾向がある。また、前記上限値以下とすることでレジスト感度が下がらない傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．０１～１．０質量％が好ましく、０．０１～０．７質量％がより好ましく、０．０５～０．５質量％がさらに好ましく、０．０５～０．３質量％が特に好ましい。 Examples of such surfactants include TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), and KP340. (Manufactured by Shinetsu Silicone), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Dow Corning), DS-401 (manufactured by Daikin) , L-77 (manufactured by Nippon Unicar) and FC4430 (manufactured by 3M Japan). As the surfactant, one type may be used, or two or more types may be used in combination in any combination and ratio.
When the photosensitive resin composition in the present invention contains a surfactant, the content ratio of the surfactant in the photosensitive resin composition is not particularly limited, but 0.01 in the total solid content in the photosensitive resin composition. By mass or more is preferable, 0.05% by mass or more is more preferable, 1.0% by mass or less is preferable, 0.7% by mass or less is more preferable, 0.5% by mass or less is further preferable, and 0.3 by mass. Mass% or less is particularly preferable. When the value is equal to or higher than the lower limit, the resist coating uniformity tends to be improved. Further, when the value is not more than the upper limit, the resist sensitivity tends not to decrease.
The above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferable, 0.01 to 0.7% by mass is more preferable, 0.05 to 0.5% by mass is further preferable, and 0.05 to 0.3% by mass is preferable. Especially preferable.
＜顔料誘導体＞
　本発明における感光性樹脂組成物には、分散性、保存性向上のため、顔料誘導体を含有させてもよい。顔料誘導体としては例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、キノフタロン系、イソインドリノン系、ジオキサジン系、アントラキノン系、インダンスレン系、ペリレン系、ペリノン系、ジケトピロロピロール系、ジオキサジン系の誘導体が挙げられるが、中でもフタロシアニン系、キノフタロン系が好ましい。 <Pigment derivative>
The photosensitive resin composition in the present invention may contain a pigment derivative in order to improve dispersibility and storage stability. Pigment derivatives include, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindoleinone-based, dioxazine-based, anthraquinone-based, indanthrone-based, perylene-based, perinone-based, and diketopyrrolopyrrole-based. , Dioxazine-based derivatives, among which phthalocyanine-based and quinophthalone-based derivatives are preferable.
　顔料誘導体の置換基としてはスルホン酸基、スルホンアミド基及びその４級塩、フタルイミドメチル基、ジアルキルアミノアルキル基、水酸基、カルボキシ基、アミド基等が顔料骨格に直接又はアルキル基、アリール基、複素環基等を介して結合したものが挙げられ、好ましくはスルホン酸基である。またこれら置換基は一つの顔料骨格に複数置換していてもよい。顔料誘導体の具体例としてはフタロシアニンのスルホン酸誘導体、キノフタロンのスルホン酸誘導体、アントラキノンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、ジケトピロロピロールのスルホン酸誘導体、ジオキサジンのスルホン酸誘導体が挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 As the substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group, an amide group and the like are directly on the pigment skeleton or an alkyl group, an aryl group or a complex. Examples thereof include those bonded via a ring group or the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted into one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivative, quinophthalone sulfonic acid derivative, anthraquinone sulfonic acid derivative, quinacridone sulfonic acid derivative, diketopyrrolopyrrole sulfonic acid derivative, and dioxazine sulfonic acid derivative. These may be used alone or in combination of two or more.
　本発明における感光性樹脂組成物が顔料誘導体を含有する場合、顔料誘導体の配合割合は特に限定されないが、感光性樹脂組成物の全固形分に対して０．１質量％以上が好ましく、０．５質量％以上がより好ましく、１．０質量％以上がさらに好ましく、また、１０質量％以下が好ましく、５質量％以下がより好ましい。前記下限値以上とすることで分散安定性が向上する傾向がある。また、前記上限値以下とすることで現像性が良好となる傾向がある。
　上記の上限及び下限は任意に組み合わせることができる。例えば、０．１～１０質量％が好ましく、０．５～１０質量％がより好ましく、１．０～５質量％がさらに好ましい。 When the photosensitive resin composition in the present invention contains a pigment derivative, the blending ratio of the pigment derivative is not particularly limited, but is preferably 0.1% by mass or more with respect to the total solid content of the photosensitive resin composition. 5% by mass or more is more preferable, 1.0% by mass or more is further preferable, 10% by mass or less is preferable, and 5% by mass or less is more preferable. When the value is equal to or higher than the lower limit, the dispersion stability tends to be improved. Further, when the value is not more than the upper limit value, the developability tends to be good.
The above upper and lower limits can be combined arbitrarily. For example, 0.1 to 10% by mass is preferable, 0.5 to 10% by mass is more preferable, and 1.0 to 5% by mass is further preferable.
＜感光性樹脂組成物の物性＞
　本発明における感光性樹脂組成物は、ブラックマトリックス形成用に好適に使用することができ、係る観点からは黒色を呈していることが好ましい。また、その塗膜の膜厚１μｍ当たりの光学濃度（ＯＤ）は１．０以上が好ましく、２．０以上がより好ましく、２．５以上がさらに好ましく、３．０以上がよりさらに好ましく、４．０以上が特に好ましく、４．５以上が最も好ましく、通常６．０以下であり、例えば、１．０～６．０が好ましく、２．０～６．０がより好ましく、２．５～６．０がさらに好ましく、３．０～６．０がよりさらに好ましく、４．０～６．０が特に好ましく、４．５～６．０が最も好ましい。前記下限値以上とすることで十分な遮光性が確保できる傾向がある。 <Physical characteristics of the photosensitive resin composition>
The photosensitive resin composition in the present invention can be suitably used for forming a black matrix, and from such a viewpoint, it is preferably black. The optical density (OD) per 1 μm of the coating film is preferably 1.0 or more, more preferably 2.0 or more, further preferably 2.5 or more, still more preferably 3.0 or more, and 4 9.0 or more is particularly preferable, 4.5 or more is most preferable, and usually 6.0 or less, for example, 1.0 to 6.0 is preferable, 2.0 to 6.0 is more preferable, and 2.5 to 6.0. 6.0 is even more preferred, 3.0 to 6.0 is even more preferred, 4.0 to 6.0 is particularly preferred, and 4.5 to 6.0 is most preferred. By setting the value to the lower limit or more, there is a tendency that sufficient light-shielding property can be ensured.
＜感光性樹脂組成物の製造方法＞
　本発明の感光性樹脂組成物の製造方法は、（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤を含む感光性樹脂組成物の製造方法であって、（Ａ）アルカリ可溶性樹脂として、本発明の製造方法で製造されたカルボキシ基含有樹脂含有液を配合することを含む。なお、本発明の製造方法で製造される感光性樹脂組成物は（Ｄ）色材を含んでもよい。
　本発明における感光性樹脂組成物は、例えば、以下の方法で製造される。
　本発明の感光性樹脂組成物が（Ｄ）色材を含有する場合、（Ｄ）色材は、予めペイントコンディショナー、サンドグラインダー、ボールミル、ロールミル、ストーンミル、ジェットミル、ホモジナイザー等を用いて分散処理することが好ましい。分散処理により（Ｄ）色材が微粒子化されるため、レジストの塗布特性が向上する。また、（Ｄ）色材として黒色色材を使用した場合は遮光能力の向上に寄与する。 <Manufacturing method of photosensitive resin composition>
The method for producing a photosensitive resin composition of the present invention is a method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator. A) The alkali-soluble resin includes a carboxy group-containing resin-containing liquid produced by the production method of the present invention. The photosensitive resin composition produced by the production method of the present invention may contain (D) a coloring material.
The photosensitive resin composition in the present invention is produced, for example, by the following method.
When the photosensitive resin composition of the present invention contains (D) a coloring material, the (D) coloring material is previously dispersed using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. It is preferable to do so. Since the (D) coloring material is made into fine particles by the dispersion treatment, the coating characteristics of the resist are improved. Further, when a black color material is used as the (D) color material, it contributes to the improvement of the light-shielding ability.
　分散処理は、（Ｄ）色材、有機溶媒、及び必要に応じて分散剤、（Ａ）アルカリ可溶性樹脂の一部又は全部を併用した系にて行うことが好ましい。（以下、分散処理に供する混合物、及び分散処理にて得られた組成物を「インク」又は「顔料分散液」と称することがある。）特に分散剤として高分子分散剤を用いると、得られたインク及びレジストの経時の増粘が抑制される（分散安定性に優れる）ので好ましい。
　感光性樹脂組成物に配合する全成分を含有する液に対して分散処理を行った場合、分散処理時に生じる発熱のため、高反応性の成分が変性する可能性がある。従って、高分子分散剤を含む系にて分散処理を行うことが好ましい。 The dispersion treatment is preferably carried out in a system in which (D) a coloring material, an organic solvent, and if necessary, a dispersant and (A) a part or all of an alkali-soluble resin are used in combination. (Hereinafter, the mixture to be subjected to the dispersion treatment and the composition obtained by the dispersion treatment may be referred to as "ink" or "pigment dispersion liquid".) In particular, when a polymer dispersant is used as the dispersant, it is obtained. It is preferable because the thickening of the ink and the resist over time is suppressed (excellent in dispersion stability).
When a liquid containing all the components to be blended in the photosensitive resin composition is subjected to the dispersion treatment, the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.
　サンドグラインダーで（Ｄ）色材を分散させる場合には、０．１～８ｍｍ程度の径のガラスビーズ又はジルコニアビーズが好ましく用いられる。分散処理条件は、温度は通常、０℃から１００℃であり、好ましくは、室温から８０℃の範囲である。分散時間は液の組成及び分散処理装置のサイズ等により適正時間が異なるため適宜調節する。レジストの２０度鏡面光沢度（ＪＩＳ　Ｚ８７４１）が１００～２００の範囲となるように、インクの光沢を制御するのが分散の目安である。レジストの光沢度が低い場合には、分散処理が十分でなく荒い顔料（色材）粒子が残っていることが多く、現像性、密着性、解像性等が不十分となる可能性がある。また、光沢値が上記範囲を超えるまで分散処理を行うと、顔料が破砕して超微粒子が多数生じるため、却って分散安定性が損なわれる傾向がある。 When the (D) coloring material is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions are such that the temperature is usually 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the liquid, the size of the dispersion treatment device, etc., and is appropriately adjusted. The guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, etc. .. Further, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.
　次に、感光性樹脂組成物中に含まれる成分、すなわち（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤、並びに（Ｄ）色材を含む場合は、上記分散処理により得られたインク等を配合し、２０～３０℃の温度で混合して均一な溶液とする。感光性樹脂組成物の製造工程においては、微細なゴミが液中に混じることが多いため、得られたレジストはフィルター等により濾過処理するのが望ましい。 Next, when the components contained in the photosensitive resin composition, that is, (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator, and (D) a coloring material are contained, the above The ink or the like obtained by the dispersion treatment is blended and mixed at a temperature of 20 to 30 ° C. to obtain a uniform solution. In the manufacturing process of the photosensitive resin composition, fine dust is often mixed in the liquid, so it is desirable to filter the obtained resist with a filter or the like.
［インク］
　本発明のインクの製造方法は、（Ａ）アルカリ可溶性樹脂、有機溶媒及び（Ｄ）色材を含むインクの製造方法であり、（Ａ）アルカリ可溶性樹脂として、本発明の製造方法で製造されるカルボキシ基含有樹脂含有液を配合することを含む。インクには、必要に応じて、分散剤を配合してもよい。
　また、本発明のインクは、（Ａ）アルカリ可溶性樹脂、有機溶媒及び（Ｄ）色材を含有し、（Ａ）アルカリ可溶性樹脂として、本発明のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含む。本発明のインクは、必要に応じて、分散剤を配合してもよい。
　以下、本発明のインクの製造方法で製造されるインク及び本発明のインクを合わせて「本発明におけるインク」と称する。
　有機溶媒、（Ｄ）色材及び分散剤は、感光性樹脂組成物で用いられるものを好ましく用いることができる。 [ink]
The method for producing an ink of the present invention is a method for producing an ink containing (A) an alkali-soluble resin, an organic solvent and (D) a coloring material, and is produced as (A) an alkali-soluble resin by the production method of the present invention. Includes blending a carboxy group-containing resin-containing liquid. A dispersant may be added to the ink, if necessary.
Further, the ink of the present invention contains (A) an alkali-soluble resin, an organic solvent and (D) a coloring material, and the (A) alkali-soluble resin contains a carboxy group derived from the carboxy group-containing resin-containing liquid of the present invention. Contains resin. The ink of the present invention may contain a dispersant, if necessary.
Hereinafter, the ink produced by the method for producing an ink of the present invention and the ink of the present invention are collectively referred to as "ink in the present invention".
As the organic solvent, (D) coloring material and dispersant, those used in the photosensitive resin composition can be preferably used.
＜インクの製造方法＞
　本発明におけるインクは、例えば、感光性樹脂組成物の製造方法で記載した分散処理にて得られる。 <Ink manufacturing method>
The ink in the present invention can be obtained, for example, by the dispersion treatment described in the method for producing a photosensitive resin composition.
［硬化物］
　本発明の硬化物の製造方法は、本発明の製造方法で得られた感光性樹脂組成物を硬化させることを含む。
　また、本発明の硬化物は、本発明の感光性樹脂組成物を硬化してなる。
　感光性樹脂組成物を硬化してなる硬化物は、画素、ブラックマトリックスや着色スペーサーなどのカラーフィルターを構成する部材として好適に用いることができる。 [Cursed product]
The method for producing a cured product of the present invention includes curing the photosensitive resin composition obtained by the production method of the present invention.
Further, the cured product of the present invention is obtained by curing the photosensitive resin composition of the present invention.
The cured product obtained by curing the photosensitive resin composition can be suitably used as a member constituting a color filter such as a pixel, a black matrix or a colored spacer.
［ブラックマトリックス］
　本発明のブラックマトリックスの製造方法は、本発明の製造方法で得られた硬化物を用いてブラックマトリックスを形成することを含む。
　また、本発明のブラックマトリックスは、本発明の感光性樹脂組成物を用いて形成されてなる。
　本発明の製造方法で得られた硬化物又は本発明の硬化物を用いたブラックマトリックスについて、その製造方法に従って説明する。 [Black Matrix]
The method for producing a black matrix of the present invention includes forming a black matrix using the cured product obtained by the production method of the present invention.
Further, the black matrix of the present invention is formed by using the photosensitive resin composition of the present invention.
The cured product obtained by the production method of the present invention or the black matrix using the cured product of the present invention will be described according to the production method.
（１）支持体
　ブラックマトリックスを形成するための支持体としては、適度の強度があれば、その材質は特に限定されるものではない。おもに透明基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレートなどのポリエステル系樹脂、ポリプロピレン、ポリエチレンなどのポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォンなどの熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリル系樹脂などの熱硬化性樹脂シート、各種ガラスが挙げられる。この中でも、耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にＩＴＯ、ＩＺＯ等の透明電極が成膜されていてもよい。透明基板以外、例えば、ＴＦＴアレイ上に形成することも可能である。 (1) Support The material of the support for forming the black matrix is not particularly limited as long as it has an appropriate strength. A transparent substrate is mainly used, and as the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethylmethacrylate and polysulphon, and epoxy resin. , A heat-curable resin sheet such as unsaturated polyester resin and poly (meth) acrylic resin, and various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance. Further, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. Other than the transparent substrate, it can be formed on, for example, a TFT array.
　支持体には、接着性などの表面物性の改良のため、必要に応じ、コロナ放電処理、オゾン処理、大気圧プラズマ処理、シランカップリング剤や、ウレタン系樹脂などの各種樹脂の薄膜形成処理を行ってもよい。
　透明基板の厚さは、通常０．０５～１０ｍｍ、好ましくは０．１～７ｍｍの範囲とされる。また各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常０．０１～１０μｍ、好ましくは０．０５～５μｍの範囲である。 In order to improve the surface physical properties such as adhesiveness, the support is subjected to corona discharge treatment, ozone treatment, atmospheric pressure plasma treatment, silane coupling agent, and thin film formation treatment of various resins such as urethane resin, if necessary. You may go.
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When the thin film forming treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.
（２）ブラックマトリックス
　本発明の製造方法で得られた硬化物又は本発明の硬化物により、ブラックマトリックスを形成する方法としては、本発明の製造方法で得られた感光性樹脂組成物または本発明の感光性樹脂組成物を硬化させて得られる硬化物でブラックマトリックスを形成する方法が挙げられる。例えば、透明基板上に本発明における感光性樹脂組成物を塗布して乾燥した後、乾燥試料の上にフォトマスクを置き、フォトマスクを介して画像露光、現像、必要に応じて熱硬化あるいは光硬化することによりブラックマトリックスを形成させる方法がある。 (2) Black Matrix As a method for forming a black matrix from the cured product obtained by the production method of the present invention or the cured product of the present invention, the photosensitive resin composition obtained by the production method of the present invention or the present invention is used. Examples thereof include a method of forming a black matrix with a cured product obtained by curing the photosensitive resin composition of the above. For example, after applying the photosensitive resin composition of the present invention on a transparent substrate and drying it, a photomask is placed on a dried sample, and image exposure, development, heat curing or light as necessary is performed through the photomask. There is a method of forming a black matrix by curing.
（３）ブラックマトリックスの形成
（３－１）感光性樹脂組成物の塗布
　ブラックマトリックス用の感光性樹脂組成物の透明基板上への塗布は、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、又はスプレーコート法などによって行うことができる。中でも、ダイコート法によれば、塗布液使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミストなどの影響が全くなく、異物発生が抑制されるなど、総合的な観点から好ましい。 (3) Formation of Black Matrix (3-1) Application of Photosensitive Resin Composition The application of the photosensitive resin composition for black matrix on a transparent substrate is performed by a spinner method, a wire bar method, a flow coat method, or a die coat method. , The roll coating method, the spray coating method, or the like. Above all, according to the die coating method, the amount of coating liquid used is significantly reduced, and there is no influence of mist or the like adhering when the spin coating method is used, and the generation of foreign substances is suppressed. It is preferable from.
　塗膜の厚さは、乾燥後の膜厚として、通常０．２～１０μｍの範囲とするのが好ましく、より好ましいのは０．５～６μｍの範囲、さらに好ましいのは１～４μｍの範囲である。前記上限値以下とすることで、パターン現像が容易となり、液晶セル化工程でのギャップ調整も容易となる傾向がある。前記下限値以上とすることで、所望の色発現が容易となる傾向がある。 The thickness of the coating film is usually preferably in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and further preferably in the range of 1 to 4 μm as the film thickness after drying. be. By setting the value to the upper limit or less, pattern development tends to be easy, and gap adjustment in the liquid crystal cell formation step tends to be easy. By setting the value to the lower limit or more, the desired color expression tends to be facilitated.
（３－２）塗膜の乾燥
　基板に感光性樹脂組成物を塗布した後の塗膜の乾燥は、ホットプレート、ＩＲオーブン、又はコンベクションオーブンを使用した乾燥法によるのが好ましい。乾燥の条件は、前記溶媒成分の種類、使用する乾燥機の性能などに応じて適宜選択することができる。乾燥時間は、溶媒成分の種類、使用する乾燥機の性能などに応じて、通常は、４０～２００℃の温度で１５秒～５分間の範囲で選ばれ、好ましくは５０～１３０℃の温度で３０秒～３分間の範囲で選ばれる。 (3-2) Drying of coating film Drying of the coating film after applying the photosensitive resin composition to the substrate is preferably by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component, the performance of the dryer used, and the like. It is selected in the range of 30 seconds to 3 minutes.
　乾燥温度は、高いほど透明基板に対する塗膜の接着性が向上するが、高すぎるとアルカリ可溶性樹脂が分解し、熱重合を誘発して現像不良を生ずる場合がある。なお、この塗膜の乾燥工程は、温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法であってもよい。 The higher the drying temperature, the better the adhesiveness of the coating film to the transparent substrate, but if it is too high, the alkali-soluble resin may decompose, inducing thermal polymerization and causing development defects. The step of drying the coating film may be a vacuum drying method in which the coating film is dried in a reduced pressure chamber without raising the temperature.
（３－３）露光
　画像露光は、感光性樹脂組成物の塗膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外域から可視域に至る波長の光を照射して行う。この際、必要に応じ、酸素による光重合性層の感度の低下を防ぐため、光重合性の塗膜上にポリビニルアルコール層などの酸素遮断層を形成した後に露光を行ってもよい。上記の画像露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアークなどのランプ光源などが挙げられる。特定の波長の光を照射して使用する場合には、光学フィルターを利用することもできる。 (3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on a coating film of a photosensitive resin composition and irradiating light having a wavelength from the ultraviolet region to the visible region through the mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film. The light source used for the above image exposure is not particularly limited. Examples of the light source include a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and a carbon arc. An optical filter can also be used when irradiating light of a specific wavelength for use.
（３－４）現像
　本発明におけるブラックマトリックスは、感光性樹脂組成物による塗膜を、上記の光源によって画像露光を行った後、有機溶剤、又は、界面活性剤とアルカリ性化合物とを含む水溶液を用いる現像によって、基板上に画像を形成して作製することができる。この水溶液には、さらに有機溶剤、緩衝剤、錯化剤、染料又は顔料を含ませることができる。 (3-4) Development In the black matrix of the present invention, a coating film made of a photosensitive resin composition is subjected to image exposure with the above-mentioned light source, and then an organic solvent or an aqueous solution containing a surfactant and an alkaline compound is used. Depending on the development used, an image can be formed and produced on the substrate. The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
　アルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウムなどの無機アルカリ性化合物や、モノ－、ジ－又はトリエタノールアミン、モノ－、ジ－又はトリメチルアミン、モノ－、ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－、ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリンなどの有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、１種単独で用いてもよく、２種以上の混合物であってもよい。 Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and phosphorus. Inorganic alkaline compounds such as potassium acid, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- Or trimethylamine, mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Examples include organic alkaline compounds. These alkaline compounds may be used alone or as a mixture of two or more.
　界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類などのノニオン系界面活性剤、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類などのアニオン性界面活性剤、アルキルベタイン類、アミノ酸類などの両性界面活性剤が挙げられる。 Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールが挙げられる。有機溶剤は、単独で用いてもよく、また、水溶液と併用してもよい。
　現像処理の条件は特に制限はなく、通常、現像温度は１０～５０℃の範囲、中でも１５～４５℃、特に好ましくは２０～４０℃で、現像方法は、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法などのいずれかの方法によることができる。 Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.
The conditions of the development process are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., particularly preferably 15 to 45 ° C., particularly preferably 20 to 40 ° C., and the development methods are a dip development method, a spray development method, and a brush. Any method such as a developing method or an ultrasonic developing method can be used.
（３－５）熱硬化処理
　現像の後の基板には、熱硬化処理又は光硬化処理、好ましくは熱硬化処理を施す。この際の熱硬化処理条件は、温度は１００～２８０℃の範囲、好ましくは１５０～２５０℃の範囲で選ばれ、時間は５～６０分間の範囲で選ばれる。
　以上のようにして形成させたブラックマトリックスの高さは通常０．５～５μｍ、好ましくは０．８～４μｍである。
　さらに、厚さ１μｍ当たりの光学濃度（ＯＤ）が２．０以上、好ましくは２．５以上、より好ましくは３．０以上、特に好ましくは３．２以上である。 (3-5) Thermosetting Treatment The developed substrate is subjected to a thermosetting treatment or a photocuring treatment, preferably a thermosetting treatment. The thermosetting treatment conditions at this time are selected in the range of 100 to 280 ° C., preferably 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.
The height of the black matrix formed as described above is usually 0.5 to 5 μm, preferably 0.8 to 4 μm.
Further, the optical density (OD) per 1 μm of thickness is 2.0 or more, preferably 2.5 or more, more preferably 3.0 or more, and particularly preferably 3.2 or more.
［その他のカラーフィルターの形成］
　ブラックマトリックスを設けた透明基板上に、上記（３－１）～（３－５）と同じプロセスで赤色、緑色、青色のうち一色の色材を含有する感光性樹脂組成物を塗布し、乾燥した後、塗膜の上にフォトマスクを重ね、このフォトマスクを介して画像露光、現像、必要に応じて熱硬化又は光硬化により画素画像を形成させ、着色層を作成する。この操作を、赤色、緑色、青色の三色の感光性樹脂組成物についてそれぞれ行うことによって、カラーフィルターを形成することができる。これらの順番は上記に限定されるものではない。 [Formation of other color filters]
A photosensitive resin composition containing one of red, green, and blue coloring materials is applied onto a transparent substrate provided with a black matrix by the same process as in (3-1) to (3-5) above, and dried. After that, a photomask is superposed on the coating film, and a pixel image is formed through the photomask by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter can be formed by performing this operation on each of the three color photosensitive resin compositions of red, green, and blue. These orders are not limited to the above.
［着色スペーサー］
　本発明の製造方法で得られた感光性樹脂組成物又は本発明の感光性樹脂組成物は、ブラックマトリックス以外に着色スペーサー用のレジストとして使用することも可能である。スペーサーをＴＦＴ型ＬＣＤに使用する場合、ＴＦＴに入射する光によりスイッチング素子としてＴＦＴが誤作動を起こすことがあり、着色スペーサーはこれを防止するために用いられ、例えば、日本国特開平８－２３４２１２号公報にスペーサーを遮光性とすることが記載されている。着色スペーサーは着色スペーサー用のマスクを用いる以外は前述のブラックマトリックスと同様の方法で形成することができる。 [Colored spacer]
The photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention can also be used as a resist for a colored spacer in addition to the black matrix. When the spacer is used for the TFT type LCD, the TFT may malfunction as a switching element due to the light incident on the TFT, and the colored spacer is used to prevent this. For example, Japanese Patent Application Laid-Open No. 8-234212 The publication describes that the spacer has a light-shielding property. The colored spacer can be formed by the same method as the above-mentioned black matrix except that a mask for the colored spacer is used.
（３－６）透明電極の形成
　カラーフィルターは、このままの状態で画像上にＩＴＯなどの透明電極を形成して、カラーディスプレー、液晶表示装置などの部品の一部として使用されるが、表面平滑性や耐久性を高めるため、必要に応じ、画像上にポリアミド、ポリイミドなどのトップコート層を設けることもできる。また一部、平面配向型駆動方式（ＩＰＳモード）などの用途においては、透明電極を形成しないこともある。 (3-6) Formation of transparent electrode A color filter forms a transparent electrode such as ITO on an image in this state and is used as a part of parts such as a color display and a liquid crystal display device, but the surface is smooth. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image in order to improve the properties and durability. Further, in some applications such as a plane alignment type drive system (IPS mode), a transparent electrode may not be formed.
［隔壁］
　本発明の製造方法で得られた感光性樹脂組成物又は本発明の感光性樹脂組成物は、隔壁、特に有機電界発光素子の有機層を区画するための隔壁を形成するために用いることも可能である。有機電界発光素子に用いる有機層としては、例えば日本国特開２０１６－１６５３９６号公報に記載されているような、正孔注入層、正孔輸送層あるいは正孔注入層上の正孔輸送層に用いる有機層が挙げられる。 [Septum]
The photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention can also be used to form a partition wall, particularly a partition wall for partitioning an organic layer of an organic electric field light emitting element. Is. Examples of the organic layer used for the organic electroluminescent device include a hole injection layer, a hole transport layer, or a hole transport layer on a hole injection layer as described in Japanese Patent Application Laid-Open No. 2016-165396. Examples include the organic layer used.
　本発明の製造方法で得られた感光性樹脂組成物又は本発明の感光性樹脂組成物を用いた隔壁について、その製造方法に従って説明する。 The photosensitive resin composition obtained by the production method of the present invention or the partition wall using the photosensitive resin composition of the present invention will be described according to the production method.
（４－１）支持体
　隔壁を形成するための支持体及び基板としては、上述した、ブラックマトリックスを形成するための支持体及び基板と同様のものを用いることができる。 (4-1) Support As the support and substrate for forming the partition wall, the same support and substrate as described above for forming the black matrix can be used.
（４－２）隔壁
　以下、隔壁として使用される場合について、本発明の製造方法で得られた感光性樹脂組成物又は本発明の感光性樹脂組成物を用いた隔壁の形成方法の具体例に従って説明する。 (4-2) Septum Hereinafter, when used as a partition wall, according to a specific example of the photosensitive resin composition obtained by the production method of the present invention or the method for forming a partition wall using the photosensitive resin composition of the present invention. explain.
　通常、隔壁が設けられるべき基板上に、感光性樹脂組成物を、塗布等の方法により膜状あるいはパターン状に供給し、溶媒を乾燥させる。続いて、露光－現像を行うフォトリソグラフィー法等の方法によりパターン形成を行う。その後、必要により追露光や熱硬化処理を行うことにより、基板上に隔壁が形成される。 Normally, the photosensitive resin composition is supplied in the form of a film or a pattern on a substrate on which a partition wall should be provided by a method such as coating, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method that performs exposure-development. After that, a partition wall is formed on the substrate by performing additional exposure and thermosetting treatment as necessary.
（４－３）隔壁の形成
　本発明の製造方法で得られた感光性樹脂組成物又は本発明の感光性樹脂組成物を用いた隔壁の形成方法における、基板への感光性樹脂組成物の供給方法、乾燥方法、露光方法、現像方法、追露光及び熱硬化処理の具体的方法は、上述したブラックマトリックスの形成と同様の方法を採用することができる。 (4-3) Formation of partition wall The supply of the photosensitive resin composition to the substrate in the method for forming the partition wall using the photosensitive resin composition obtained by the production method of the present invention or the photosensitive resin composition of the present invention. As a specific method, a drying method, an exposure method, a developing method, a follow-up exposure and a thermosetting treatment, the same method as the above-mentioned black matrix formation can be adopted.
　隔壁として使用する場合の大きさや形状等は、これを適用する有機電界発光素子の仕様等によって適宜調整されるが、感光性樹脂組成物より形成される隔壁の高さは通常０．５～１０μｍ程度である。 The size and shape of the partition wall when used as a partition wall are appropriately adjusted depending on the specifications of the organic electroluminescent device to which the partition wall is applied, but the height of the partition wall formed from the photosensitive resin composition is usually 0.5 to 10 μm. Degree.
［有機電界発光素子］
　本発明の有機電界発光素子は、本発明の硬化物、例えば隔壁を備える。
　例えば、上述した方法により製造された隔壁パターンを備える基板を用いて、種々の有機電界発光素子が製造される。有機電界発光素子を形成する方法は特に限定されないが、好ましくは、上述した方法により基板上に隔壁のパターンを形成した後に、機能材料を真空状態で昇華させ、基板上の隔壁により囲まれた領域内に付着させて成膜する蒸着法や、キャスト法、スピンコート法、インクジェット印刷法といったウェットプロセスにて画素等の有機層を形成することによって、有機電界発光素子が製造される。 [Organic electroluminescent device]
The organic electroluminescent device of the present invention comprises a cured product of the present invention, for example, a partition wall.
For example, various organic electroluminescent devices are manufactured using a substrate having a partition wall pattern manufactured by the above method. The method for forming the organic electric field light emitting device is not particularly limited, but preferably, after forming the pattern of the partition wall on the substrate by the above-mentioned method, the functional material is sublimated in a vacuum state and the region surrounded by the partition wall on the substrate. An organic electric field light emitting device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method in which a film is formed by adhering to the inside, a casting method, a spin coating method, or an inkjet printing method.
　有機電界発光素子のタイプとしては、ボトムエミッション型やトップエミッション型が挙げられる。
　ボトムエミッション型では、例えば、透明電極を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に正孔輸送層、発光層、電子輸送層、金属電極層を積層して作成される。一方でトップエミッション型では、例えば、金属電極層を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に電子輸送層、発光層、正孔輸送層、透明電極層を積層して作成される。
　発光層としては、日本国特開２００９－１４６６９１号公報や日本国特許第５７３４６８１号公報に記載されているような有機電界発光層が挙げられる。また、日本国特許第５６５３３８７号公報や日本国特許第５６５３１０１号公報に記載されているような量子ドットを用いてもよい。 Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which transparent electrodes are laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. To. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall. Is created.
Examples of the light emitting layer include an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
　層構成はこれに限定されず、例えば、正孔輸送層、電子輸送層の各層は発光効率の観点から二層以上からなる積層構成でもよい。各層の厚みは特に限定されないが、発光効率や輝度の観点から、通常１～５００ｎｍである。 The layer structure is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and brightness.
　有機電界発光素子は、開口部ごとにＲＧＢ各色を分けて形成してもよく、１つの開口部に二色以上を積層してもよい。有機電界発光素子は信頼性向上の観点から、封止層を備えていてもよい。封止層は空気中の水分が有機電界発光素子に吸着し、発光効率を低下することを防ぐ機能を有する。有機電界発光素子は、光取り出し効率向上の観点から、空気との界面に低反射膜を備えていてもよい。低反射膜を空気と素子との界面に配置することで屈折率のギャップを小さくし、界面での反射を抑制することが期待できる。このような低反射膜には、例えば、モスアイ構造、超多層膜の技術が適用されうる。 The organic electroluminescent element may be formed by separating each RGB color for each opening, or two or more colors may be laminated in one opening. The organic electroluminescent device may be provided with a sealing layer from the viewpoint of improving reliability. The sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and lowering the luminous efficiency. The organic electroluminescent device may be provided with a low reflection film at the interface with air from the viewpoint of improving the light extraction efficiency. By arranging the low-reflection film at the interface between the air and the element, it can be expected that the gap in the refractive index is reduced and the reflection at the interface is suppressed. For such a low-reflection film, for example, a technique of a moth-eye structure or a super-multilayer film can be applied.
　有機電界発光素子を画像表示装置の画素として使用する場合には、ある画素の発光層の光が他の画素に漏れることを防止する必要があり、さらに、電極等が金属である場合には外光の反射に伴う画像品質の低下を防止する必要があるため、有機電界発光素子を構成する隔壁に遮光性を付与することが好ましい。
　有機電界発光素子においては、隔壁の上面及び下面に電極を付与することが必要であるため、絶縁性の観点から、隔壁は高抵抗、低誘電率であることが好ましい。そのため、隔壁に遮光性を付与するために着色剤を使用する場合には、高抵抗かつ低誘電率である前記有機顔料を用いることが好ましい。 When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light emitting layer of one pixel from leaking to another pixel, and further, when the electrode or the like is made of metal, it is outside. Since it is necessary to prevent deterioration of image quality due to light reflection, it is preferable to impart light-shielding property to the partition wall constituting the organic electroluminescent element.
In an organic electroluminescent device, it is necessary to provide electrodes on the upper surface and the lower surface of the partition wall. Therefore, from the viewpoint of insulating properties, the partition wall preferably has high resistance and low dielectric constant. Therefore, when a colorant is used to impart light-shielding properties to the partition wall, it is preferable to use the organic pigment having high resistance and low dielectric constant.
［画像表示装置］
　本発明の画像表示装置の製造方法は、本発明の製造方法で得られた硬化物、又は本発明の製造方法で得られたブラックマトリックスを用いることを特徴とする。
　また、本発明の画像表示装置は、本発明の硬化物、又は本発明のブラックマトリックスを備える。本発明における画像表示装置は、本発明における感光性樹脂組成物を硬化させた硬化物を有するものであり、その製造方法としては、例えば、本発明の製造方法で得られた感光性樹脂組成物又は本発明の感光性樹脂組成物により形成された、硬化物、ブラックマトリクスや隔壁を用いる製造方法が挙げられる。
　本発明における画像表示装置としては、画像や映像を表示する装置であれば特に限定は受けないが、後述する液晶表示装置や有機ＥＬディスプレイが挙げられる。 [Image display device]
The method for manufacturing an image display device of the present invention is characterized by using a cured product obtained by the manufacturing method of the present invention or a black matrix obtained by the manufacturing method of the present invention.
Further, the image display device of the present invention includes the cured product of the present invention or the black matrix of the present invention. The image display device in the present invention has a cured product obtained by curing the photosensitive resin composition in the present invention, and as a method for producing the same, for example, the photosensitive resin composition obtained by the production method in the present invention. Alternatively, a production method using a cured product, a black matrix or a partition wall formed by the photosensitive resin composition of the present invention can be mentioned.
The image display device in the present invention is not particularly limited as long as it is a device for displaying an image or a moving image, and examples thereof include a liquid crystal display device and an organic EL display described later.
［液晶表示装置］
　本発明における液晶表示装置は、本発明におけるブラックマトリックスを有するものであり、カラー画素やブラックマトリックスの形成順序や形成位置等、特に制限を受けるものではない。 [Liquid crystal display device]
The liquid crystal display device in the present invention has the black matrix in the present invention, and is not particularly limited in terms of the formation order and formation position of the color pixels and the black matrix.
　液晶表示装置は、通常、カラーフィルター上に配向膜を形成し、この配向膜上にスペーサーを散布した後、対向基板と貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入し、対向電極に結線して完成する。配向膜としては、ポリイミド等の樹脂膜が好適である。配向膜の形成には、通常、グラビア印刷法及び／又はフレキソ印刷法が採用され、配向膜の厚さは数１０ｎｍとされる。熱焼成によって配向膜の硬化処理を行った後、紫外線の照射やラビング布による処理によって表面処理し、液晶の傾きを調整しうる表面状態に加工される。 A liquid crystal display device usually forms an alignment film on a color filter, sprays a spacer on the alignment film, attaches the spacer to the facing substrate to form a liquid crystal cell, and injects liquid crystal into the formed liquid crystal cell. It is completed by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. A gravure printing method and / or a flexographic printing method is usually adopted for forming the alignment film, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by heat firing, it is surface-treated by irradiation with ultraviolet rays or treatment with a rubbing cloth to obtain a surface state in which the inclination of the liquid crystal can be adjusted.
　スペーサーとしては、対向基板とのギャップ（隙間）に応じた大きさのものが用いられ、通常２～８μｍのものが好適である。カラーフィルター基板上に、フォトリソグラフィー法によって透明樹脂膜のフォトスペーサー（ＰＳ）を形成し、これをスペーサーの代わりに活用することもできる。対向基板としては、通常、アレイ基板が用いられ、特にＴＦＴ（薄膜トランジスタ）基板が好適である。 As the spacer, a spacer having a size corresponding to the gap (gap) with the facing substrate is used, and a spacer having a size of 2 to 8 μm is usually preferable. A photospacer (PS) of a transparent resin film can be formed on a color filter substrate by a photolithography method, and this can be used instead of the spacer. As the facing substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly suitable.
　対向基板との貼り合わせのギャップは、液晶表示装置の用途によって異なるが、通常２～８μｍの範囲で選ばれる。対向基板と貼り合わせた後、液晶注入口以外の部分は、エポキシ樹脂等のシール材によって封止する。シール材は、ＵＶ照射及び／又は加熱することによって硬化させ、液晶セル周辺がシールされる。
　周辺をシールされた液晶セルは、パネル単位に切断した後、真空チャンバー内で減圧とし、上記液晶注入口を液晶に浸漬した後、チャンバー内をリークすることによって、液晶を液晶セル内に注入する。液晶セル内の減圧度は、通常、１×１０-2～１×１０-7Ｐａであるが、好ましくは１×１０-3～１×１０-6Ｐａである。また、減圧時に液晶セルを加温するのが好ましく、加温温度は通常３０～１００℃であり、より好ましくは５０～９０℃である。減圧時の加温保持は、通常１０～６０分間の範囲とされ、その後液晶中に浸漬される。液晶を注入した液晶セルは、液晶注入口を、ＵＶ硬化樹脂を硬化させて封止することによって、液晶表示装置（パネル）が完成する。 The gap for bonding to the facing substrate varies depending on the application of the liquid crystal display device, but is usually selected in the range of 2 to 8 μm. After bonding to the facing substrate, the parts other than the liquid crystal injection port are sealed with a sealing material such as epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then depressurized in a vacuum chamber, the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber leaks to inject the liquid crystal into the liquid crystal cell. .. The degree of decompression in the liquid crystal cell is usually 1 × 10 −2 to 1 × 10 -7 Pa, but preferably 1 × 10 -3 to 1 × 10 -6 Pa. Further, it is preferable to heat the liquid crystal cell at the time of depressurization, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The warming retention at the time of depressurization is usually in the range of 10 to 60 minutes, and then immersed in the liquid crystal display. A liquid crystal display device (panel) is completed by sealing the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin and sealing the liquid crystal injection port.
　液晶の種類には特に制限がなく、芳香族系、脂肪族系、多環状化合物等、従来から知られている液晶であって、リオトロピック液晶、サーモトロピック液晶等のいずれでもよい。サーモトロピック液晶には、ネマティック液晶、スメスティック液晶及びコレステリック液晶等が知られているが、いずれであってもよい。 The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic type, an aliphatic type, or a polycyclic compound, and may be any of a liotropic liquid crystal, a thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, a nematic liquid crystal, a smestic liquid crystal, a cholesteric liquid crystal and the like are known, but any of them may be used.
［有機ＥＬディスプレイ］
　本発明における有機ＥＬディスプレイは、本発明におけるカラーフィルターや本発明における有機電界発光素子を用いて作製されたものである。 [Organic EL display]
The organic EL display in the present invention is manufactured by using the color filter in the present invention and the organic electroluminescent element in the present invention.
　本発明におけるカラーフィルターを用いて有機ＥＬディスプレイを作製する場合、例えば図１に示すように、まず透明支持基板１０上に、感光性樹脂組成物により形成されたパターン（すなわち、画素２０、及び隣接する画素２０の間に設けられた樹脂ブラックマトリックス（図示せず））が形成されてなるカラーフィルターを作製し、該カラーフィルター上に有機保護層３０及び無機酸化膜４０を介して有機発光体５００を積層することによって、有機ＥＬ素子１００を作製することができる。なお、画素２０及び樹脂ブラックマトリックスの内、少なくとも一つは本発明の感光性樹脂組成物を用いて作製されたものである。有機発光体５００の積層方法としては、カラーフィルター上面へ透明陽極５０、正孔注入層５１、正孔輸送層５２、発光層５３、電子注入層５４、及び陰極５５を逐次形成していく方法や、別基板上へ形成した有機発光体５００を無機酸化膜４０上に貼り合わせる方法などが挙げられる。このようにして作製された有機ＥＬ素子１００を用い、例えば「有機ＥＬディスプレイ」（オーム社，２００４年８月２０日発光，時任静士、安達千波矢、村田英幸著）に記載された方法等にて、有機ＥＬディスプレイを作製することができる。 When an organic EL display is manufactured using the color filter of the present invention, for example, as shown in FIG. 1, a pattern formed by a photosensitive resin composition (that is, pixels 20 and adjacent to each other) is first placed on a transparent support substrate 10. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is produced, and an organic illuminant 500 is formed on the color filter via an organic protective layer 30 and an inorganic oxide film 40. The organic EL element 100 can be manufactured by laminating the above. At least one of the pixel 20 and the resin black matrix was produced by using the photosensitive resin composition of the present invention. As a method of laminating the organic illuminant 500, a method of sequentially forming a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. Using the organic EL element 100 thus produced, for example, the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Luminous, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. , An organic EL display can be manufactured.
　なお、本発明におけるカラーフィルターは、パッシブ駆動方式の有機ＥＬディスプレイにもアクティブ駆動方式の有機ＥＬディスプレイにも適用可能である。 The color filter in the present invention can be applied to both a passive drive type organic EL display and an active drive type organic EL display.
［カルボキシ基含有樹脂の安定化方法］
　本発明のカルボキシ基含有樹脂の安定化方法は、エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させて得られる、カルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液に、水を添加することを含む。
　詳細は、本発明のカルボキシ基含有樹脂含有液の製造方法における工程Ｂと同様である。 [Method for stabilizing carboxy group-containing resin]
The method for stabilizing the carboxy group-containing resin of the present invention comprises a reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid dianhydride (c). It comprises adding water to a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin obtained by reacting the polybasic acid monoanhydride (d) in an organic solvent.
The details are the same as in step B in the method for producing the carboxy group-containing resin-containing liquid of the present invention.
　カルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液を得る際には、エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）と、多価アルコール（ｅ）とを有機溶媒中で反応させて得てもよい。
　エポキシ化合物（ａ）、不飽和一塩基酸（ｂ）、多塩基酸二無水物（ｃ）、多塩基酸一無水物（ｄ）、多価アルコール（ｅ）の好ましい種類や好ましい配合量等は、カルボキシ基含有樹脂含有液の製造方法で前述した種類や配合量等と同様である。
　カルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液を得るための反応に用いられる有機溶媒としては、本発明のカルボキシ基含有樹脂含有液の製造方法で用いられる有機溶媒を好ましく用いることができる。 When obtaining a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, a reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b) and a polybasic acid dianhydride. (C) may be obtained by reacting the polybasic acid monoanhydride (d) with the polyhydric alcohol (e) in an organic solvent.
Preferred types and amounts of the epoxy compound (a), unsaturated monobasic acid (b), polybasic acid dianhydride (c), polybasic acid monoanhydride (d), polyhydric alcohol (e), etc. , The method for producing a carboxy group-containing resin-containing liquid is the same as the above-mentioned type and blending amount.
As the organic solvent used in the reaction for obtaining the carboxy group-containing resin-containing liquid containing the carboxy group-containing resin, the organic solvent used in the method for producing the carboxy group-containing resin-containing liquid of the present invention can be preferably used.
　実施例を挙げて本発明をより具体的に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
＜実施例１～３：カルボキシ基含有樹脂含有液（１）～（３）の製造＞ <Examples 1 to 3: Production of carboxy group-containing resin-containing liquids (1) to (3)>
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　上記構造のエポキシ化合物（エポキシ当量２４０）２８５０ｇ、アクリル酸８６２ｇ、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）２５０６ｇ、トリフェニルホスフィン４５ｇ、及びパラメトキシフェノール２．７ｇを温度計、攪拌機、冷却管を取り付けたフラスコに入れ、攪拌しながら１００℃で酸価が５ｍｇＫＯＨ／ｇ以下になるまで９時間反応させ、中間体を含む中間体溶液を得た。
　上記により得られた中間体溶液に、トリメチロールプロパン（ＴＭＰ）４１ｇ、ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）１３５３ｇ、テトラヒドロフタル酸無水物（ＴＨＰＡ）２５ｇ、及びＰＧＭＥＡ５２６１ｇを加え、攪拌しながら１０５℃で２０時間反応させ、第一のカルボキシ基含有樹脂含有液を得た。
　得られた第一のカルボキシ基含有樹脂含有液を５０℃まで冷却した後に、含有水分量をカールフィッシャー水分計（京都電子工業社製、ＭＫＡ－６１０）で計測し、表１に記載の含有水分率になるように、５０℃のカルボキシ基含有樹脂含有液を攪拌しながら水を添加し、カルボキシ基含有樹脂含有液（１）～（３）（第二のカルボキシ基含有樹脂含有液）をそれぞれ得た。 A flask equipped with a thermometer, a stirrer, and a cooling tube containing 2850 g of an epoxy compound (epoxy equivalent 240) having the above structure, 862 g of acrylic acid, 2506 g of propylene glycol monomethyl ether acetate (PGMEA), 45 g of triphenylphosphine, and 2.7 g of paramethoxyphenol. The mixture was reacted with stirring at 100 ° C. for 9 hours until the acid value became 5 mgKOH / g or less to obtain an intermediate solution containing an intermediate.
To the intermediate solution obtained above, 41 g of trimethylolpropane (TMP), 1353 g of biphenyltetracarboxylic acid dianhydride (BPDA), 25 g of tetrahydrophthalic acid anhydride (THPA), and 5261 g of PGMEA were added, and the temperature was 105 ° C. with stirring. The reaction was carried out for 20 hours to obtain a first carboxy group-containing resin-containing solution.
After cooling the obtained first carboxy group-containing resin-containing liquid to 50 ° C., the water content was measured with a Karl Fisher Moisture Meter (MKA-610, manufactured by Kyoto Denshi Kogyo Co., Ltd.), and the water content shown in Table 1 was measured. Water is added while stirring the carboxy group-containing resin-containing liquid at 50 ° C., and the carboxy group-containing resin-containing liquids (1) to (3) (second carboxy group-containing resin-containing liquid) are added, respectively. Obtained.
＜比較例１：カルボキシ基含有樹脂含有液（４）の製造＞
　第一のカルボキシ基含有樹脂含有液を得た後、水を添加しなかったこと以外は、実施例１～３と同じ方法で、カルボキシ基含有樹脂含有液（４）を得た。 <Comparative Example 1: Production of Liquid (4) Containing Resin with Carboxy Group>
After obtaining the first carboxy group-containing resin-containing liquid, the carboxy group-containing resin-containing liquid (4) was obtained by the same method as in Examples 1 to 3 except that water was not added.
（経時安定性）
　実施例１～３及び比較例１で得られたカルボキシ基含有樹脂含有液（１）～（４）のポリスチレン換算の重量平均分子量（Ｍｗ）と樹脂溶液の粘度を、それぞれＧＰＣ（Ｗａｔｅｒｓ社製、２６９５）と粘度計（東機産業社製、ＲＥ－８０Ｌ）で測定した。測定結果を表１に示す。
　また、実施例１～３及び比較例１で得られたカルボキシ基含有樹脂含有液（１）～（４）を３５℃で１４日間保管した後、各カルボキシ基含有樹脂のＭｗ及び樹脂溶液の粘度を計測し、経時安定性を以下の基準で評価した。評価結果を表１に示す。 (Stability over time)
The polystyrene-equivalent weight average molecular weight (Mw) of the carboxy group-containing resin-containing liquids (1) to (4) obtained in Examples 1 to 3 and Comparative Example 1 and the viscosity of the resin solution were determined by GPC (Watters), respectively. 2695) and a viscometer (RE-80L, manufactured by Toki Sangyo Co., Ltd.). The measurement results are shown in Table 1.
Further, after storing the carboxy group-containing resin-containing liquids (1) to (4) obtained in Examples 1 to 3 and Comparative Example 1 at 35 ° C. for 14 days, the Mw of each carboxy group-containing resin and the viscosity of the resin solution Was measured, and the stability over time was evaluated according to the following criteria. The evaluation results are shown in Table 1.
（重量平均分子量）
　３５℃、１４日間保管前後でのカルボキシ基含有樹脂の重量平均分子量（Ｍｗ）の変化率を下記式（Ｉ）で算出し、以下の基準で評価した。変化率が小さいほど経時安定性に優れる。
　重量平均分子量の変化率＝（３５℃で１４日間保管した後の重量平均分子量）／（保管前の重量平均分子量）×１００（％）　　・・・式（Ｉ）
　評価基準：
　　Ａ：変化率が１５０％未満
　　Ｂ：変化率が１５０％以上かつ２００％未満
　　Ｃ：変化率が２００％以上 (Weight average molecular weight)
The rate of change in the weight average molecular weight (Mw) of the carboxy group-containing resin before and after storage at 35 ° C. for 14 days was calculated by the following formula (I) and evaluated according to the following criteria. The smaller the rate of change, the better the stability over time.
Rate of change in weight average molecular weight = (weight average molecular weight after storage at 35 ° C. for 14 days) / (weight average molecular weight before storage) x 100 (%) ... Formula (I)
Evaluation criteria:
A: Change rate is less than 150% B: Change rate is 150% or more and less than 200% C: Change rate is 200% or more
（粘度）
　３５℃、１４日間保管前後での樹脂溶液の粘度の変化率を下記式（ＩＩ）で算出し、以下の基準で評価した。変化率が小さいほど経時安定性に優れる。
　粘度の変化率＝（３５℃で１４日間保管した後の粘度）／（保管前の粘度）×１００（％）　　・・・式（ＩＩ）
　評価基準：
　　Ａ：変化率が１５０％未満
　　Ｂ：変化率が１５０％以上かつ２００％未満
　　Ｃ：変化率が２００％以上 (viscosity)
The rate of change in the viscosity of the resin solution before and after storage at 35 ° C. for 14 days was calculated by the following formula (II) and evaluated according to the following criteria. The smaller the rate of change, the better the stability over time.
Viscosity change rate = (viscosity after storage at 35 ° C. for 14 days) / (viscosity before storage) x 100 (%) ... Equation (II)
Evaluation criteria:
A: Change rate is less than 150% B: Change rate is 150% or more and less than 200% C: Change rate is 200% or more
Figure JPOXMLDOC01-appb-T000028
Figure JPOXMLDOC01-appb-T000028
　表１に示した実施例１～３と比較例１により、カルボキシ基含有樹脂含有液に水を添加する工程を有することで、カルボキシ基含有樹脂含有液に含まれるカルボキシ基含有樹脂の重量平均分子量及び粘度の経時安定性を向上させることが可能であるとわかる。これは、カルボキシ基含有樹脂の合成後に水を添加することで、カルボキシ基含有樹脂が有するカルボキシ基と、カルボキシ基含有樹脂又は多価アルコールが有するヒドロキシ基との平衡反応を制御し、保管時の縮合反応による重合反応を抑制できるためと考えられる。 According to Examples 1 to 3 and Comparative Example 1 shown in Table 1, the weight average molecular weight of the carboxy group-containing resin contained in the carboxy group-containing resin-containing liquid is obtained by having the step of adding water to the carboxy group-containing resin-containing liquid. And it can be seen that it is possible to improve the stability of the viscosity over time. By adding water after the synthesis of the carboxy group-containing resin, the equilibrium reaction between the carboxy group of the carboxy group-containing resin and the hydroxy group of the carboxy group-containing resin or the polyhydric alcohol is controlled, and the equilibrium reaction is controlled during storage. This is thought to be because the polymerization reaction due to the condensation reaction can be suppressed.

Claims (28)

  1. 　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させ、第一のカルボキシ基含有樹脂含有液を得る工程Ａと、
    　前記第一のカルボキシ基含有樹脂含有液に水を添加して、第二のカルボキシ基含有樹脂含有液を得る工程Ｂとを含む、カルボキシ基含有樹脂含有液の製造方法。     A reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d) are used as an organic solvent. Step A to obtain the first carboxy group-containing resin-containing liquid by reacting in
    A method for producing a carboxy group-containing resin-containing liquid, which comprises the step B of adding water to the first carboxy group-containing resin-containing liquid to obtain a second carboxy group-containing resin-containing liquid.
  2. 　前記第二のカルボキシ基含有樹脂含有液の含有水分率が０．１質量％以上になるように、前記第一のカルボキシ基含有樹脂含有液に水を添加する、請求項１に記載のカルボキシ基含有樹脂含有液の製造方法。 The carboxy group according to claim 1, wherein water is added to the first carboxy group-containing resin-containing liquid so that the water content of the second carboxy group-containing resin-containing liquid is 0.1% by mass or more. A method for producing a liquid containing a resin.
  3. 　前記工程Ａにおいて、さらに多価アルコール（ｅ）を加えて反応させる、請求項１又は２に記載のカルボキシ基含有樹脂含有液の製造方法。 The method for producing a carboxy group-containing resin-containing liquid according to claim 1 or 2, wherein the polyhydric alcohol (e) is further added and reacted in the step A.
  4. 　前記多価アルコール（ｅ）が、トリメチロールプロパンを含む、請求項３に記載のカルボキシ基含有樹脂含有液の製造方法。 The method for producing a carboxy group-containing resin-containing liquid according to claim 3, wherein the polyhydric alcohol (e) contains trimethylolpropane.
  5. 　前記多塩基酸二無水物（ｃ）が、ビフェニルテトラカルボン酸二無水物を含む、請求項１～４のいずれか１項に記載のカルボキシ基含有樹脂含有液の製造方法。 The method for producing a carboxy group-containing resin-containing liquid according to any one of claims 1 to 4, wherein the polybasic acid dianhydride (c) contains a biphenyltetracarboxylic acid dianhydride.
  6. 　前記多塩基酸一無水物（ｄ）が、テトラヒドロフタル酸無水物を含む、請求項１～５のいずれか１項に記載のカルボキシ基含有樹脂含有液の製造方法。 The method for producing a carboxy group-containing resin-containing liquid according to any one of claims 1 to 5, wherein the polybasic acid anhydride (d) contains a tetrahydrophthalic anhydride.
  7. 　（Ａ）アルカリ可溶性樹脂、有機溶媒及び（Ｄ）色材を含むインクの製造方法であって、
    　前記（Ａ）アルカリ可溶性樹脂として、請求項１～６のいずれか１項に記載の製造方法で製造されたカルボキシ基含有樹脂含有液を配合することを含む、インクの製造方法。     A method for producing an ink containing (A) an alkali-soluble resin, an organic solvent, and (D) a coloring material.
    A method for producing an ink, which comprises blending the carboxy group-containing resin-containing liquid produced by the production method according to any one of claims 1 to 6 as the (A) alkali-soluble resin.
  8. 　（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤を含む感光性樹脂組成物の製造方法であって、
    　前記（Ａ）アルカリ可溶性樹脂として、請求項１～６のいずれか１項に記載の製造方法で製造されたカルボキシ基含有樹脂含有液を配合することを含む、感光性樹脂組成物の製造方法。     A method for producing a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable monomer, and (C) a photopolymerization initiator.
    A method for producing a photosensitive resin composition, which comprises blending the carboxy group-containing resin-containing liquid produced by the production method according to any one of claims 1 to 6 as the (A) alkali-soluble resin.
  9. 　前記感光性樹脂組成物が、さらに（Ｄ）色材を含む、請求項８に記載の感光性樹脂組成物の製造方法。 The method for producing a photosensitive resin composition according to claim 8, wherein the photosensitive resin composition further contains (D) a coloring material.
  10. 　請求項８又は９に記載の製造方法で得られた感光性樹脂組成物を硬化させることを含む、硬化物の製造方法。 A method for producing a cured product, which comprises curing the photosensitive resin composition obtained by the production method according to claim 8 or 9.
  11. 　請求項１０に記載の製造方法で得られた硬化物を用いてブラックマトリックスを形成することを含む、ブラックマトリックスの製造方法。 A method for producing a black matrix, which comprises forming a black matrix using the cured product obtained by the production method according to claim 10.
  12. 　請求項１０に記載の製造方法で得られた硬化物、又は請求項１１に記載の製造方法で得られたブラックマトリックスを用いることを特徴とする、画像表示装置の製造方法。 A method for manufacturing an image display device, which comprises using the cured product obtained by the manufacturing method according to claim 10 or the black matrix obtained by the manufacturing method according to claim 11.
  13. 　カルボキシ基含有樹脂、有機溶媒及び水を含有し、含有水分率が０．１質量％以上１質量％以下である、カルボキシ基含有樹脂含有液。 A carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, an organic solvent and water, and having a water content of 0.1% by mass or more and 1% by mass or less.
  14. 　前記カルボキシ基含有樹脂がエポキシ化合物（ａ）由来の構造を有する請求項１３に記載のカルボキシ基含有樹脂含有液。 The carboxy group-containing resin-containing liquid according to claim 13, wherein the carboxy group-containing resin has a structure derived from the epoxy compound (a).
  15. 　前記カルボキシ基含有樹脂が不飽和一塩基酸（ｂ）由来の構造を有する請求項１３又は１４に記載のカルボキシ基含有樹脂含有液。 The carboxy group-containing resin-containing liquid according to claim 13 or 14, wherein the carboxy group-containing resin has a structure derived from the unsaturated monobasic acid (b).
  16. 　前記カルボキシ基含有樹脂が多塩基酸二無水物（ｃ）由来の構造を有する請求項１３～１５のいずれか１項に記載のカルボキシ基含有樹脂含有液。 The carboxy group-containing resin-containing liquid according to any one of claims 13 to 15, wherein the carboxy group-containing resin has a structure derived from the polybasic acid dianhydride (c).
  17. 　前記カルボキシ基含有樹脂が多塩基酸一無水物（ｄ）由来の構造を有する請求項１３～１６のいずれか１項に記載のカルボキシ基含有樹脂含有液。 The carboxy group-containing resin-containing liquid according to any one of claims 13 to 16, wherein the carboxy group-containing resin has a structure derived from the polybasic acid monoanhydride (d).
  18. 　（Ａ）アルカリ可溶性樹脂、有機溶媒及び（Ｄ）色材を含有し、
    　前記（Ａ）アルカリ可溶性樹脂が、請求項１３～１７のいずれか１項に記載のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含むインク。     Contains (A) alkali-soluble resin, organic solvent and (D) coloring material,
    An ink in which the alkali-soluble resin (A) contains a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid according to any one of claims 13 to 17.
  19. 　（Ａ）アルカリ可溶性樹脂、（Ｂ）光重合性モノマー及び（Ｃ）光重合開始剤を含有し、
    　前記（Ａ）アルカリ可溶性樹脂が、請求項１３～１７のいずれか１項に記載のカルボキシ基含有樹脂含有液に由来するカルボキシ基含有樹脂を含む感光性樹脂組成物。     It contains (A) an alkali-soluble resin, (B) a photopolymerizable monomer and (C) a photopolymerization initiator.
    A photosensitive resin composition in which the alkali-soluble resin (A) contains a carboxy group-containing resin derived from the carboxy group-containing resin-containing liquid according to any one of claims 13 to 17.
  20. 　請求項１９に記載の感光性樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the photosensitive resin composition according to claim 19.
  21. 　請求項２０に記載の硬化物を用いて形成されてなるブラックマトリックス。 A black matrix formed by using the cured product according to claim 20.
  22. 　請求項２０に記載の硬化物、又は請求項２１に記載のブラックマトリックスを備える、画像表示装置。 An image display device comprising the cured product according to claim 20 or the black matrix according to claim 21.
  23. 　エポキシ化合物（ａ）と不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、多塩基酸二無水物（ｃ）と、多塩基酸一無水物（ｄ）とを有機溶媒中で反応させて得られる、カルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液に、水を添加することを含む、カルボキシ基含有樹脂の安定化方法。 A reaction product obtained by reacting an epoxy compound (a) with an unsaturated monobasic acid (b), a polybasic acid dianhydride (c), and a polybasic acid monoanhydride (d) are used as an organic solvent. A method for stabilizing a carboxy group-containing resin, which comprises adding water to a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin, which is obtained by reacting in the process.
  24. 　水を添加した後のカルボキシ基含有樹脂含有液の含有水分率が０．１質量％以上になるように水を添加する、請求項２３に記載のカルボキシ基含有樹脂の安定化方法。 The method for stabilizing a carboxy group-containing resin according to claim 23, wherein water is added so that the water content of the carboxy group-containing resin-containing liquid after the addition of water is 0.1% by mass or more.
  25. 　前記カルボキシ基含有樹脂含有液が、前記エポキシ化合物（ａ）と前記不飽和一塩基酸（ｂ）とを反応させて得られる反応生成物と、前記多塩基酸二無水物（ｃ）と、前記多塩基酸一無水物（ｄ）と、多価アルコール（ｅ）とを有機溶媒中で反応させて得られるカルボキシ基含有樹脂を含むカルボキシ基含有樹脂含有液である、請求項２３又は２４に記載のカルボキシ基含有樹脂の安定化方法。 The reaction product obtained by reacting the epoxy compound (a) with the unsaturated monobasic acid (b), the polybasic acid dianhydride (c), and the above-mentioned carboxy group-containing resin-containing liquid. 23 or 24, which is a carboxy group-containing resin-containing liquid containing a carboxy group-containing resin obtained by reacting a polybasic acid monoanhydride (d) with a polyhydric alcohol (e) in an organic solvent. A method for stabilizing a carboxy group-containing resin.
  26. 　前記多価アルコール（ｅ）が、トリメチロールプロパンを含む、請求項２５に記載のカルボキシ基含有樹脂の安定化方法。 The method for stabilizing a carboxy group-containing resin according to claim 25, wherein the polyhydric alcohol (e) contains trimethylolpropane.
  27. 　前記多塩基酸二無水物（ｃ）が、ビフェニルテトラカルボン酸二無水物を含む、請求項２３～２６のいずれか１項に記載のカルボキシ基含有樹脂の安定化方法。 The method for stabilizing a carboxy group-containing resin according to any one of claims 23 to 26, wherein the polybasic acid dianhydride (c) contains a biphenyltetracarboxylic acid dianhydride.
  28. 　前記多塩基酸一無水物（ｄ）が、テトラヒドロフタル酸無水物を含む、請求項２３～２７のいずれか１項に記載のカルボキシ基含有樹脂の安定化方法。 The method for stabilizing a carboxy group-containing resin according to any one of claims 23 to 27, wherein the polybasic acid monoanhydride (d) contains a tetrahydrophthalic anhydride.
PCT/JP2021/038749 2020-10-30 2021-10-20 Method for producing carboxy-group-containing resin-containing solution and method for stabilizing carboxy-group-containing resin WO2022091905A1 (en)

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JP2001350260A (en) * 2000-06-05 2001-12-21 Toppan Printing Co Ltd Photosensitive resin, composition and method for preparing the same
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