WO2022124296A1 - 感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置 - Google Patents

感光性樹脂組成物、硬化物、ブラックマトリックス及び画像表示装置 Download PDF

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WO2022124296A1
WO2022124296A1 PCT/JP2021/044876 JP2021044876W WO2022124296A1 WO 2022124296 A1 WO2022124296 A1 WO 2022124296A1 JP 2021044876 W JP2021044876 W JP 2021044876W WO 2022124296 A1 WO2022124296 A1 WO 2022124296A1
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mass
group
preferable
resin composition
photosensitive resin
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PCT/JP2021/044876
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English (en)
French (fr)
Japanese (ja)
Inventor
知子 砂留
和裕 中谷
貴裕 宮崎
貴志 野口
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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Priority to JP2022568286A priority Critical patent/JPWO2022124296A1/ja
Priority to KR1020237019040A priority patent/KR20230117134A/ko
Priority to CN202180082473.9A priority patent/CN116568717A/zh
Publication of WO2022124296A1 publication Critical patent/WO2022124296A1/ja
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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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a photosensitive resin composition, a cured product, a black matrix (Black Matrix, hereinafter abbreviated as "BM”), and an image display device.
  • BM Black Matrix
  • a color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic, and then pixels of three or more different colors such as red, green, and blue are sequentially arranged in a grid pattern and stripes. 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.
  • the pigment dispersion method is known as a typical manufacturing method for color filters.
  • a color filter is manufactured by the pigment dispersion method
  • a photosensitive resin composition containing a black pigment such as carbon black is first applied onto a transparent substrate, dried under reduced pressure in a vacuum drying device, and then heated and dried in a hot plate.
  • BM is formed by curing (curing) by a high temperature treatment of 200 ° C. or higher, and this is repeated for each color such as red, green, and blue to form pixels.
  • BM is formed by curing (curing) by a high temperature treatment of 200 ° C. or higher, and this is repeated for each color such as red, green, and blue to form pixels.
  • the BM is generally arranged in a grid pattern, a stripe pattern, or a mosaic pattern between pixels such as red, green, and blue, and has a role of improving contrast or preventing light leakage by suppressing color mixing between the pixels. .. Therefore, the BM is required to have a high light-shielding property. Further, since the edge portion of the pixels such as red, green, and blue formed after the BM is partially overlapped with the BM, a step is formed at the overlapped portion due to the influence of the film thickness of the BM. At this overlapping portion, the flatness of the pixels is impaired, non-uniformity of the liquid crystal cell gap or disorder of the orientation of the liquid crystal occurs, which causes a decrease in display capability.
  • the output of the backlight tends to be low, and the thin line of BM, which is a light-shielding part, can display images with high brightness even under such conditions. Is being promoted.
  • miniaturization such as tablets has become the mainstream, while the demand for high resolution is increasing in large-sized televisions. For these reasons, the demand for higher definition of BM is increasing, and in recent years, BM thin lines with a line width of about 6 to 8 ⁇ m have been required from the conventional line width of about 10 ⁇ m. It's coming.
  • the fine line width is 10 ⁇ m or more, the fine line adhesion with the substrate can be maintained even if an insertion of about 1 to 2 ⁇ m occurs on one side of the BM fine line (a total of about 2 to 4 ⁇ m on both sides of the thin line), but the line width is 10 ⁇ m. If the fine line pattern is less than, the contact area of the BM / substrate interface becomes small, so that the decrease in the fine line adhesion becomes remarkably large every time the line width is narrowed by 1 ⁇ m.
  • the frame part was conventionally formed separately, and a sealant was applied to it and attached to the array substrate.
  • a method has come to be used in which a frame portion is formed at the same time, and a sealing agent is applied to the frame portion and bonded to the frame portion. Therefore, more than before, the contact stress between the color filter substrate and the BM is required.
  • Patent Document 1 describes a photosensitive resin composition containing an organosilicon compound having a specific structure and a surfactant exhibiting specific physical characteristics.
  • Patent Document 2 describes a photosensitive resin composition containing 20% to 80% of a monomer having a caprolactone structure in the molecule among all photopolymerizable monomers.
  • an object of the present invention is to provide a photosensitive resin composition excellent in fine wire adhesion, adhesion stress, and suppression of pin unevenness during hot plate drying.
  • the present inventors have found that the above-mentioned problems can be solved by using a specific alkali-soluble resin, a specific photopolymerizable monomer, and a specific surfactant. That is, the gist of the present invention lies below.
  • a photosensitive resin composition containing (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, and (e) a surfactant.
  • the alkali-soluble resin (a) contains an alkali-soluble resin (a1) having a partial structure represented by the following general formula (a1-1).
  • the photopolymerizable monomer (b) contains a photopolymerizable monomer (b6) having a partial structure represented by the following general formula (b5).
  • the surfactant (e) is characterized by containing a surfactant (e1) having a surface tension of a 0.5 mass% propylene glycol monomethyl ether acetate solution at 23 ° C. of 23.0 mN / m or less. Sex resin composition.
  • R 7 represents a hydrogen atom or a methyl group.
  • N represents a repeating unit. * Each represents a bond.
  • R 1 represents an alkylene group having 2 to 6 carbon atoms which may have a substituent
  • R 2 represents a hydrogen atom or a methyl group
  • m represents an integer of 1 to 3. Represents. * Represents a bond.
  • R b is a group shown in the general formula (b5)
  • R c is a group shown in the formula (b7)
  • p2 is an integer of 1 to 6, and * indicates a bond. .
  • (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 solvent contained in the photosensitive resin composition or the ink described later. Even if the components other than the solvent are liquid at room temperature, the components are not included in the solvent and are included in the total solid content.
  • 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 photosensitive resin composition of the present invention contains (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator and (e) a surfactant, and (a) an alkali-soluble resin is described below.
  • the monomer (b6) is contained, and the (e) surfactant contains a surfactant (e1) having a surface tension of a 0.5 mass% propylene glycol monomethyl ether acetate solution at 23 ° C. of 23.0 mN / m or less. ..
  • R 7 represents a hydrogen atom or a methyl group.
  • N represents a repeating unit. * Each represents a bond.
  • R 1 represents an alkylene group having 2 to 6 carbon atoms which may have a substituent
  • R 2 represents a hydrogen atom or a methyl group
  • m represents an integer of 1 to 3. Represents. * Represents a bond.
  • the photosensitive resin composition of the present invention may contain a dispersant, a thiol, an adhesion improver, a pigment derivative, and a compounding component such as a development improver, an ultraviolet absorber, and an antioxidant, if necessary. It is preferable that each compounding component is used in a state of being dissolved or dispersed in an organic solvent.
  • the photosensitive resin composition of the present invention contains (a) an alkali-soluble resin.
  • the alkali-soluble resin is particularly limited as long as 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.
  • an alkali-soluble resin having a carboxy group is preferable.
  • an alkali-soluble resin having an ethylenically unsaturated group is preferable, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxy group is more preferable.
  • the alkali-soluble resin (a) in the present invention includes an alkali-soluble resin (a1) having a partial structure represented by the following general formula (a1-1).
  • a1-1 alkali-soluble resin having a partial structure represented by the following general formula (a1-1).
  • R 7 represents a hydrogen atom or a methyl group.
  • N represents a repeating unit. * Each represents a bond.
  • the repeating unit represented by n is preferably an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 from the viewpoint of sensitivity.
  • R 7 is preferably a hydrogen atom.
  • X is preferably directly bonded from the viewpoint of sensitivity.
  • the content ratio of the alkali-soluble resin (a1) in the alkali-soluble resin is preferably 10% by mass or more, more preferably 30% by mass or more, and 50% by mass. % Or more is further preferable, 70% by mass or more is further preferable, and 90% by mass or more is particularly preferable. Further, from the viewpoint of the linearity of the pattern, 100% by mass or less is preferable, 99% by mass or less is more preferable, and 98% by mass or less is further preferable. The above upper and lower limits can be combined arbitrarily. For example, 10 to 100% by mass is preferable, 30 to 100% by mass is more preferable, 50 to 99% by mass is further preferable, 70 to 99% by mass is further preferable, and 90 to 98% by mass is particularly preferable.
  • the alkali-soluble resin (a1) having a partial structure represented by the formula (a1-1) is obtained by adding (meth) acrylic acid to, for example, an epoxy resin having a cardo skeleton represented by the following structural formula (a7-1). It is preferably an alkali-soluble resin obtained by reacting with a polybasic acid and / or an anhydride thereof.
  • benzene ring in formula (a7-1) may be further substituted with any substituent.
  • n represents an integer of 0 to 4, preferably 0 to 3, more preferably 0 to 2, and even more preferably 0.
  • a known method can be used as a method for adding (meth) acrylic acid to the epoxy resin.
  • the reaction can be carried out at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst.
  • the catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride.
  • Quaternary ammonium salts such as dodecyltrimethylammonium chloride can be used.
  • the amount of (meth) acrylic 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, with respect to 1 equivalent of the epoxy group of the epoxy resin.
  • the amount of (meth) acrylic acid is preferably at least the above lower limit, the amount of unsaturated group introduced is sufficient, the subsequent reaction with polybasic acid and / or its anhydride is sufficient, and a large amount of epoxy group is used. There is a tendency to suppress the residual of.
  • the amount to be used to be equal to or less than the upper limit, it tends to be possible to suppress the residual (meth) acrylic acid as an unreacted product.
  • polybasic acid and / or its anhydride examples include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid and methylhexa. Included is one or more selected from hydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • a known method can also be used for the addition reaction of polybasic acid and / or its anhydride, and the desired product can be obtained by continuing the reaction under the same conditions as the addition reaction of (meth) acrylic acid. ..
  • the alkali-soluble resin (a1) is, for example, after mixing a polybasic acid and / or its anhydride with a reaction product of an epoxy resin and (meth) acrylic acid, or after mixing an epoxy resin with (meth) acrylic acid. It is obtained by mixing the reaction product with a polybasic acid and / or its anhydride and a polyhydric alcohol, and then heating the reaction product. In this case, the mixing order of the polybasic acid and / or its anhydride and the polyhydric alcohol is not particularly limited. Upon heating, the polybasic acid and / or its anhydride undergoes an addition reaction with any hydroxyl group present in the mixture of the reaction product with (meth) acrylic acid and the polyhydric alcohol.
  • the amount of the polyhydric alcohol used is the reaction product of the epoxy resin and (meth) acrylic acid, and the polybasic acid and / or its anhydride from the viewpoint of exhibiting the effect while suppressing thickening and gelation. It is preferably about 0.01 to 0.5 times by mass, more preferably about 0.02 to 0.2 times by mass with respect to the reaction product.
  • alkali-soluble resin (a1) one type may be used alone, or two or more types of resins may be mixed and used.
  • the acid value of the alkali-soluble resin (a1) is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, further preferably 80 mgKOH / g or more, and preferably 200 mgKOH / g or less, and 150 mgKOH / g or less. Is more preferable, and 120 mgKOH / g or less is further preferable.
  • the value is equal to or higher than the lower limit, the residue tends to be reduced. Further, by setting the value to the upper limit or less, there is a tendency that the fine line adhesion can be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 200 mgKOH / g is preferable, 50 to 150 mgKOH / g is more preferable, and 80 to 120 mgKOH / g is further preferable.
  • the weight average molecular weight (Mw) in terms of polystyrene as measured by gel permeation chromatography (GPC) of the alkali-soluble resin (a1) is preferably 1,000 or more, more preferably 2,000 or more, and 4 It is more preferably 5,000 or more, and particularly preferably 5,000 or more. Further, it is preferably 20,000 or less, more preferably 15,000 or less, further preferably 10,000 or less, further preferably 8,000 or less, and 7,000 or less. Is particularly preferable. When it is set to the lower limit or more, the fine wire adhesion and the adhesion stress with the substrate 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 photosensitive resin composition of the present invention may contain an alkali-soluble resin other than the alkali-soluble resin (a1).
  • the alkali-soluble resin other than the alkali-soluble resin (a1) the solubility of the exposed portion and the non-exposed portion in alkali development changes after the coating film obtained by applying and drying the photosensitive resin composition is exposed.
  • the alkali-soluble resin having a carboxy group is preferable.
  • an alkali-soluble resin having an ethylenically unsaturated group is preferable, and an alkali-soluble resin having an ethylenically unsaturated group and a carboxy group is more preferable.
  • Specific examples thereof include an epoxy (meth) acrylate resin (a2) having a carboxy group other than the alkali-soluble resin (a1), an acrylic copolymer resin (a3), and other resins (a4).
  • Epoxy (meth) acrylate resin (a2) having a carboxy group other than the alkali-soluble resin (a1) examples include the following epoxy (meth) acrylate resin (a2-1) and / or epoxy (meth) acrylate resin (a2). -2) can be mentioned.
  • ⁇ Epoxy (meth) acrylate resin (a2-2)> An ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is added to the epoxy resin, and further reacted with a polyhydric alcohol and a polybasic acid and / or its anhydride. The resulting alkali-soluble resin.
  • the epoxy resin as a raw material 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.
  • Epoxy resin for example, "EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.
  • Epoxy resin can be preferably used.
  • "XD-1000” manufactured by Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a1)
  • Nippon Kayaku Co., Ltd. is used as the epoxy resin represented by the following general formula (a2).
  • "NC-3000" can be mentioned.
  • 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. Indicates an alkyl group having 1 to 12 carbon atoms which may be used, or a phenyl group which may have a substituent. Further, the * mark in the formula represents the bond in (a3).
  • R 51 to R 54 are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups 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. It should be noted that the plurality of R 23s existing in one molecule may be the same or different from each other.
  • an epoxy resin represented by any of the general formulas (a1) to (a3), (a5), or (a6).
  • Examples of the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having an ⁇ , ⁇ -unsaturated monocarboxylic acid or a carboxy group include (meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, and m-vinylbenzoic acid.
  • p-vinylbenzoic acid ⁇ -position haloalkyl of (meth) acrylic acid, monocarboxylic acids such as alkoxyl, halogen, nitro, cyano-substituted, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloy Loxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloy Loxypropyl succinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxy Propy
  • (meth) acrylic acid ester for example, lactones such as ⁇ -caprolactone, ⁇ -propiolactone, ⁇ -butyrolactone, and ⁇ -valerolactone are added to (meth) acrylic acid to have one hydroxyl group at the end.
  • a monomer; or a monomer having one hydroxyl group at the end such as hydroxyalkyl (meth) acrylate; or a compound having one hydroxyl group at the end such as pentaerythritol tri (meth) acrylate (anhydrous).
  • (meth) acrylic acid is particularly preferable.
  • a known method can be used as a method for adding an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to the epoxy resin.
  • an esterification catalyst an ⁇ , ⁇ -unsaturated monocarboxylic acid or an ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group can be reacted with an epoxy resin at a temperature of 50 to 150 ° C. can.
  • the catalyst used here includes tertiary phosphines such as triethylphosphine, tributylphosphine, tricyclohexylphosphine and triphenylphosphine, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine and benzyldiethylamine, tetramethylammonium chloride and tetraethylammonium chloride.
  • Quaternary ammonium salts such as dodecyltrimethylammonium chloride can be used.
  • the epoxy resin ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst, one type may be used alone or two types may be used. The above may be used together.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin. , 0.7 to 1.1 equivalents are more preferred.
  • the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group By setting the amount of ⁇ , ⁇ -unsaturated monocarboxylic acid or ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group to the above lower limit or more, the amount of unsaturated group introduced becomes sufficient, and the subsequent polybasic acid And / or its reaction with the anhydride is sufficient, and there is a tendency that a large amount of residual epoxy group can be suppressed.
  • the amount to be used by setting the amount to be used to the upper limit or less, it is possible to suppress the ⁇ , ⁇ -unsaturated monocarboxylic acid or the ⁇ , ⁇ -unsaturated monocarboxylic acid ester having a carboxy group from remaining as an unreacted product. Tend.
  • the same compound as the alkali-soluble resin (a1) can be used. Further, as the synthesis method, the same synthesis method as that of the alkali-soluble resin (a1) can be used.
  • the acid value of the epoxy (meth) acrylate resin (a2-1, a2-2) thus obtained is preferably 10 mgKOH / g or more, more preferably 50 mgKOH / g or more, still more preferably 80 mgKOH / g or more. Further, it is preferably 200 mgKOH / g or less, 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.
  • the polystyrene-equivalent weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (a2-1, a2-2) measured by gel permeation chromatography (GPC) is preferably 1,000 or more, more preferably 1,500 or more. It is preferable, more preferably 2,000 or more, and particularly preferably 2,300 or more. Further, 20,000 or less is preferable, 15,000 or less is more preferable, 10,000 or less is further preferable, 8,000 or less is further preferable, and 6,000 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 when the value is not more than the upper limit, the developability and resolubility tend to be good.
  • the above upper and lower limits can be combined arbitrarily. For example, 1,000 to 20,000 is preferable, 1,000 to 15,000 is more preferable, 1,500 to 10,000 is more preferable, 2,000 to 8,000 is even more preferable, and 2,300 to 8,000. 6,000 is particularly preferred.
  • acrylic copolymer resin (a3) examples include Japanese Patent Laid-Open No. 7-2072111, Japanese Patent Application Laid-Open No. 8-259876, Japanese Patent Application Laid-Open No. 10-300922, and Japanese Patent Application Laid-Open No. 11-140144.
  • the following resins (a3-1) to (a3-4) are preferable, and the resin of (a3-1) is particularly preferable.
  • (A3-1) 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.
  • Resin (a3-3) Resin in which an epoxy group-containing unsaturated compound is added to the carboxy group portion of the resin of (a3-2)
  • (a3-4) (meth) acrylic resin.
  • the other alkali-soluble resin (a4) is alkali-soluble except for the alkali-soluble resin (a1), the epoxy (meth) acrylate resin (a2) having a carboxy group other than the alkali-soluble resin (a1), and the acrylic copolymer resin (a3).
  • a resin there is no particular limitation, and it may be selected from the resins usually used for the photosensitive resin composition for a color filter.
  • the alkali-soluble resins described in Japanese Patent Application Laid-Open No. 2007-27172, Japanese Patent Application Laid-Open No. 2007-316620, and Japanese Patent Application Laid-Open No. 2007-334290 can be mentioned.
  • the content ratio of the alkali-soluble resin is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is 15% by mass or more, and particularly preferably 20% by mass or more. Further, it is preferably 90% by mass or less, more preferably 70% by mass or less, further 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.
  • the value to the upper limit or less 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 fine line 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, 15 to 30% by mass is further preferable, and 20 to 25% by mass is particularly preferable.
  • the content ratio of the alkali-soluble resin (a1) is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 10% by mass, based on the total solid content of the photosensitive resin composition of the present invention. It is 15% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, still 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.
  • the value to the upper limit or less 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 fine line 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.
  • the content ratio of the alkali-soluble resin (a1) with respect to the total content of the alkali-soluble resin is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably. Is 90% by mass or more. Further, it is preferably 100% by mass or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 100% by mass is preferable, 30 to 100% by mass is more preferable, 50 to 100% by mass is further preferable, and 90 to 100% by mass is particularly preferable.
  • the content of the (a) alkali-soluble resin with respect to 100 parts by mass of the photopolymerizable monomer is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, still more preferably 200 parts by mass or more. Further, 1000 parts by mass or less is preferable, 800 parts by mass or more is more preferable, 600 parts by mass or more is further preferable, and 400 parts by mass or more is particularly preferable. When it is at least the above lower limit value, the solubility of the unexposed portion in the developing solution tends to be good. Further, when the value is not more than the upper limit, excessive penetration of the developing solution into the exposed portion can be suppressed, and the sharpness and fine line adhesion of the image tend to be improved. The above upper and lower limits can be combined arbitrarily. For example, 100 to 1000 parts by mass is preferable, 100 to 800 parts by mass is more preferable, 150 to 600 parts by mass is further preferable, and 200 to 400 parts by mass is particularly preferable.
  • the photosensitive resin composition of the present invention contains (b) a photopolymerizable monomer from the viewpoint of sensitivity and the like.
  • Examples of the (b) photopolymerizable monomer used in the present invention 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 ester, acrylonitrile, styrene and a carboxylic acid having one ethylenically unsaturated bond, and an ester of a polyvalent or monovalent alcohol.
  • the (b) photopolymerizable monomer used in the present invention includes a photopolymerizable monomer (b6) having a partial structure represented by the following general formula (b5).
  • R 1 represents an alkylene group having 2 to 6 carbon atoms which may have a substituent
  • R 2 represents a hydrogen atom or a methyl group
  • m represents an integer of 1 to 3. Represents. * Represents a bond.
  • the photopolymerizable monomer (b6) having the partial structure represented by (b5) used in the present invention is represented by any of the following general formulas (b1) to (b4). It is preferable to have a structure to be polymerized.
  • R b is a group shown in the formula (b5)
  • R c is a group shown in the following general formula (b7)
  • p1 is an integer of 1 to 4
  • * indicates a bond. ..
  • R 2 has the same meaning as described above, and * indicates a bond.
  • R b is a group shown in the formula (b5)
  • R c is a group shown in the formula (b7)
  • p2 is an integer of 1 to 6
  • * indicates a bond.
  • R b is a group represented by the formula (b5)
  • R c is a group represented by the formula (b7)
  • R 8 is an alkyl group having 1 to 6 carbon atoms
  • p3 is 1 to 1 to. It is an integer of 3, and * indicates a bond.
  • R b is a group represented by the formula (b5)
  • R c is a group represented by the formula (b7)
  • R 9 is an alkylene group having 1 to 10 carbon atoms and 7 to 10 carbon atoms. It is an arylene alkylene group or an arylene group having 6 to 10 carbon atoms.
  • the plurality of R9s existing in one molecule may be the same or different from each other.
  • p4 is an integer of 1 to 3, and * indicates a bond.
  • R 1 represents an alkylene group in which the main chain may have branches having 2 to 6 carbon atoms, and R 2 represents a hydrogen atom or a methyl group.
  • m represents an integer of 1 to 3.
  • the plurality of R 1s may be the same or different.
  • R 1 represents an alkylene group that may have branches of the main chain having 2 to 6 carbon atoms.
  • the carbon number thereof is preferably 3 or more, more preferably 4 or more, preferably 6 or less, and more preferably 5 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 3 to 6 is preferable, and 4 to 5 is more preferable.
  • the alkylene group may or may not have a branch. From the viewpoint of fine wire adhesion and adhesion stress with the substrate, it is preferable that there is no branching.
  • alkylene group having a branch having 2 to 6 carbon atoms in the main chain examples include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group and a 1,4-butylene group.
  • examples thereof include 1,2-butylene group, 1,3-butylene group, 1,5-pentylene group, 1,2-pentylene group, 1,3-pentylene group, 1,6-hexylene group and cyclohexylene group. From the viewpoint of fine wire adhesion and adhesion stress with the substrate, 1,4-butylene group and 1,5-pentylene group are preferable, and 1,5-pentylene group is more preferable.
  • p1 is 1 or more, preferably 2 or more, and 4 or less, preferably 3 or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 1 to 3 is preferable, and 2 to 3 is more preferable.
  • p2 is 1 or more, preferably 2 or more, more preferably 3 or more, and 6 or less, preferably 5 or less.
  • the lower limit there is an effect of improving the adhesion stress with the substrate, and by setting it below the upper limit, it is possible to suppress excessive penetration of the developer into the exposed area, resulting in sharpness of the image and adhesion of fine lines. It has the effect of improving the sex.
  • the above upper and lower limits can be combined arbitrarily. For example, 2 to 6 is preferable, 2 to 5 is more preferable, and 3 to 5 is even more preferable.
  • R 8 in the formula (b3) is an alkyl group having 1 to 6 carbon atoms, but the carbon number is 1 or more, preferably 2 or more, and 6 or less, preferably 5 from the viewpoint of adhesion to the substrate. Hereinafter, it is more preferably 4 or less.
  • the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, a 2-butyl group, a 1-pentyl group, a 1-hexyl group and a cyclohexyl. The group is mentioned. From the viewpoint of fine wire adhesion and adhesion stress with the substrate, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable.
  • p3 is 1 or more, preferably 2 or more, and 3 or less. Setting it above the lower limit has the effect of improving adhesion, and setting it below the upper limit suppresses excessive penetration of the developer into the exposed area, resulting in good image sharpness and fine line adhesion. There is an effect.
  • the above upper and lower limits can be combined arbitrarily. For example, 2 to 3 are preferable.
  • the carbon number of the alkylene group of R 9 is 1 or more, preferably 2 or more, preferably 6 or less, and more preferably 3 or less from the viewpoint of adhesion to the substrate.
  • the alkyl group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, a 1,2-butylene group and 1,5.
  • -Pentylene group, 1,6-hexylene group, cyclohexylene group, methylenecyclohexylene group can be mentioned.
  • the arylene alkylene group of R9 has 7 or more carbon atoms, and preferably 9 or less carbon atoms from the viewpoint of adhesion to the substrate.
  • the arylene alkylene group having 7 to 10 carbon atoms include a phenylene methylene group, a phenylene ethylene group, and a phenylene propylene group.
  • a phenylene methylene group and a phenylene ethylene group are preferable, and a phenylene methylene group is more preferable.
  • the carbon number of the arylene group of R9 is 6 or more and 10 or less from the viewpoint of adhesion to the substrate.
  • the arylene group having 6 to 10 carbon atoms include a phenylene group and a naphthylene group.
  • a phenylene group is preferable from the viewpoint of adhesion to the substrate.
  • R 9 in the formula (b4) a methylene group, an ethylene group, and a propylene group are preferable, and an ethylene group is more preferable, from the viewpoint of fine wire adhesion and adhesion stress with the substrate.
  • p4 is 1 or more, preferably 2 or more, and 3 or less.
  • the photopolymerizable monomer (b6) is a commercially available product, for example, "DPCA-20", “DPCA-30”, “DPCA-60”, “DPCA-120” manufactured by Nippon Kayaku Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd. "A9300-CL1" and “A9300-CL3" are mentioned.
  • a photopolymerizable monomer other than the photopolymerizable monomer (b6) can be used.
  • the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, still more preferably 5 or more, and particularly preferably 6 or more. , And more preferably 10 or less, more preferably 8 or less.
  • 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 the polyfunctional ethylenic monomer include an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid; an aliphatic polyhydroxy compound and an aromatic polyhydroxy.
  • Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a 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, pentaerythritol triacrylate, and penta.
  • Acrylic acid esters of aliphatic polyhydroxy compounds such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate; methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylate; Examples thereof include itaconic acid esters in which the acrylates of these exemplary compounds are replaced with itaconates; crotonic acid esters in which the acrylates of these exemplary compounds are replaced with clonates; maleic acid esters in which the acrylates of these exemplary compounds are replaced with maleates.
  • ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid examples include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogalloltriacrylate. 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 Condensations of ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol and glycerin;
  • 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.
  • Acrylate esters such as; vinyl group-containing compounds such as divinylphthalate; These may be used alone or in combination of two or more.
  • the content ratio of the photopolymerizable monomer is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass, based on the total solid content of the photosensitive resin composition. % Or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit of the content ratio of the photopolymerizable monomer is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the photocuring due to ultraviolet irradiation is improved and the fine line adhesion 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 content ratio of the photopolymerizable monomer (b6) is not particularly limited, but is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass, based on the total solid content of the photosensitive resin composition. % Or less, more preferably 30% by mass or less, particularly preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit of the content ratio of the photopolymerizable monomer is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more.
  • the adhesion stress with the substrate 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 content ratio of the photopolymerizable monomer (b6) to the total content of the photopolymerizable monomer is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 80% by mass or more. Further, it is preferably 100% by mass or less. When it is at least the above lower limit value, the adhesion stress with the substrate tends to be improved.
  • the above upper and lower limits can be combined arbitrarily. For example, 30 to 100% by mass is preferable, 50 to 100% by mass is more preferable, and 80 to 100% by mass is further preferable.
  • the photosensitive resin composition of 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 Application 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.
  • 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
  • Examples thereof include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • 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 is mentioned.
  • Examples of ⁇ -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.
  • oxime derivatives are particularly preferable in terms of sensitivity.
  • an alkali-soluble resin containing a phenolic hydroxyl group it may be disadvantageous in terms of sensitivity. Therefore, oxime derivatives (oxime ester compounds and ketooxime compounds) having particularly excellent sensitivity are useful. From the viewpoint of adhesion to the substrate, an oxime ester compound is more preferable.
  • 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.
  • BM black matrix
  • 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 3 carbon atoms.
  • Cyclo alkanoyl group of 8 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, amino of 2 to 10 carbon atoms.
  • alkylcarbonyl group An alkylcarbonyl 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 hydrogen, or 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, which may be substituted 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 formula (22).
  • the R 22 in the formula (22) and the R 22a in the formula (23) are preferably an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, and a cycloalkanoyl group having 3 to 8 carbon atoms. Can be mentioned.
  • the R 21a in the formula (23) is preferably a linear alkyl group such as an unsubstituted methyl group, an ethyl group or a propyl group, or a cycloalkylalkyl group, or a propyl substituted with an N-acetyl-N-acetoxyamino group. Group is mentioned.
  • R 21b in the formula (23) include a optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, and an optionally substituted phenylsulfide group.
  • a compound in which R 21b in the 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 the substitution.
  • a carbazolyl 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. It is desirable that the substituent on the carbazolyl group (or one of the substituents if it has two or more substituents) is attached to the 3-position of the carbazolyl group.
  • Examples of 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.
  • 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-based compound examples include compounds containing a structural portion represented by the following general formula (24). Preferred examples thereof include ketooxime ester compounds represented by the following general formula (25).
  • R 24 is synonymous with R 22 in equation (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, a heteroarylalkyl group having 1 to 20 carbon atoms, respectively.
  • a heteroarylloyl group having 1 to 20, 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 23b represents any substituent, including aromatic or heteroaromatic rings.
  • 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 formula (24) and the R 24a in the formula (25) include an alkanoyl group having 2 to 12 carbon atoms, a heteroarylalkanoyl group having 1 to 20 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, and a carbon number of carbon atoms. 7 to 20 aryloyl groups are preferred.
  • R 23a in the formula (25) an unsubstituted ethyl group, a propyl group, a butyl group, an ethyl group substituted with a methoxycarbonyl group, or a propyl group is preferable.
  • R 23b in the formula (25) a optionally substituted carbazoyl group and an optionally substituted phenylsulfide group are preferable.
  • the ketooxime ester-based compound suitable for the present invention include, but are not limited to, the following compounds.
  • Examples of commercially available products of photopolymerization initiators for ketooxime ester compounds include OXE-01 manufactured by BASF and TR-PBG-305 manufactured by Joshu Strong Electronics.
  • the oxime ester-based compound and the keto-oxime ester-based compound may be, for example, one of a series of compounds described in Japanese Patent Application Laid-Open No. 2000-80068 and Japanese Patent Application Laid-Open No. 2006-36750.
  • One type of photopolymerization initiator may be used alone, or two or more types may be used in combination.
  • 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 -Anthraquinone derivatives such as chloroanthraquinone; benzophenone derivatives such as benzophenone, Michelers ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone; 2, 2-Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, ⁇ -hydroxy-2-methylphenylpropanol, 1-hydroxy-1-methylethyl
  • benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate
  • aclysine derivatives such as 9-phenylaclydin and 9- (p-methoxyphenyl) acridin
  • 9,10-dimethyl Phenazine derivatives such as benzphenazine
  • Anthron derivatives such as benzanthrone can be mentioned.
  • oxime ester derivatives are particularly preferable for the above-mentioned reasons.
  • 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 and Japanese Patent Application Laid-Open No. 4-219756; 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 and Japanese Patent Application Laid-Open No. 5-289335; Pyromethene dyes described; Japanese Patent Laid-Open No.
  • Japanese Patent Application Laid-Open No. 54-155292 Japanese Patent Application Laid-Open No. 45-373777, Japanese Patent Application Laid-Open No. 48-84183, Japan.
  • Japanese Patent Application Laid-Open No. 52-112681 Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69
  • an amino group-containing sensitizing dye is preferable, and a compound having an amino group and a phenyl group in the same molecule is more preferable.
  • the sensitizing dye include 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, and 3,3'-diaminobenzophenone.
  • the content ratio of the photopolymerization initiator is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably, with respect to the total solid content of the photosensitive resin composition of the present invention. Is 3% by mass or more, more preferably 4% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less. Particularly preferably, it is 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 adhesion stress with the substrate 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 content ratio of the oxime ester photopolymerization initiator (c1) is not particularly limited, but the photosensitive resin composition of the present invention is not particularly limited. It is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, still more preferably 4% by mass or more, based on the total solid content. Further, it is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, still more preferably 10% by mass or less, and particularly preferably 8% by mass or less.
  • the value When the value is equal to or higher than the lower limit, the sensitivity tends to be improved and the fine line adhesion is improved. 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 content ratio of the sensitizing dye is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, still more preferably 0 to 10% by mass in the total solid content of the photosensitive resin composition. %.
  • the photosensitive resin composition of the present invention preferably contains (d) a coloring material.
  • the coloring material refers to a material that colors the photosensitive resin composition of 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.
  • organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolenone, dioxazine, indanthrone, and perylene
  • various inorganic pigments can be used as the structure. 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.
  • blue pigment examples 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.
  • green pigment examples 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.
  • 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, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, 180 can be mentioned.
  • orange pigments 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 a mixture of red, green, blue and the like. 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 the carbon black include the following carbon blacks.
  • black pigments for example, 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 used in the present invention may be any as long as it can develop a desired color when used as a colored layer of a color filter, and is not particularly limited and varies depending on the type of pigment used. It is preferably in the range of about 100 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. When the pigment is carbon black, the average particle size is preferably 60 nm or less, more preferably 50 nm or less, and more preferably 20 nm or more.
  • the average particle size of the pigment can be determined 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 of the present invention preferably contains at least a pigment as the (d) coloring material, but in addition, a dye may be used in combination as long as it does not affect the effect of the present invention.
  • a dye may be used in combination as long as it does not affect the effect of the present invention. 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.
  • 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 dyes 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.
  • Examples of the phthalocyanine dye include C.I. I. Pad blue 5 can be mentioned.
  • Examples of the quinoneimine dye include C.I. I. Basic Blue 3, C.I. I. Basic blue 9 can be mentioned.
  • Examples of the quinoline dye include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 can be mentioned.
  • Examples of the nitro dye include C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 can be mentioned.
  • the photosensitive resin composition of the present invention can be used for various purposes as described above, but excellent image forming property is particularly effective when used for forming a black matrix for a color filter. ..
  • 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.
  • carbon black it is particularly preferable to use carbon black from the viewpoint of dispersion stability and light-shielding property.
  • the photosensitive resin composition of the present invention has a large effect of suppressing pin unevenness in a region where the density of the coloring material is high. Especially in recent years, it is necessary to increase the density of the coloring material in order to increase the degree of shading.
  • the content ratio of the (d) coloring material in the region where the effect is large is preferably 30% by mass or more, more preferably 40% by mass or more, and more preferably 50% by mass or more with respect to the total solid content of the photosensitive resin composition. More preferably, 52% by mass or more is particularly preferable. 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 and lower limits can be combined arbitrarily. For example, 30 to 70% by mass is preferable, 40 to 70% by mass is more preferable, 50 to 65% by mass is further preferable, and 52 to 65% by mass is particularly preferable.
  • a photosensitive resin composition having a high light-shielding property (optical density, OD value) can be obtained.
  • the optical density in the case of forming the above can be set to a value of 4.0 or more.
  • the optical density is more preferably 4.1 or more, still more preferably 4.2 or more.
  • the content ratio of (d) the coloring material is not particularly limited, but (a) 100 parts by mass of the alkali-soluble resin, preferably 20 parts by mass or more. It is more preferably 50 parts by mass or more, further preferably 100 parts by mass or more, still more preferably 120 parts by mass or more, particularly preferably 150 parts by mass or more, particularly preferably 180 parts by mass or more, and most preferably 200 parts by mass or more. Further, it is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and further preferably 250 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, and by setting it to the upper limit value or less, the fine line during development tends to be suppressed. Adhesion tends to improve.
  • the above upper and lower limits can be combined arbitrarily. For example, 20 to 500 parts by mass is preferable, 50 to 500 parts by mass is more preferable, 100 to 500 parts by mass is further preferable, 120 to 300 parts by mass is more preferable, 150 to 300 parts by mass is particularly preferable, and 180 to 250 parts is particularly preferable. Parts by mass are particularly preferable, and parts by mass of 200 to 250 are most preferable.
  • the content ratio of carbon black is not particularly limited, but from the viewpoint of obtaining a cured film having a high light-shielding property, all of the photosensitive resin compositions. It is preferably 30% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 52% by mass or more with respect to the solid content. 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 and lower limits can be combined arbitrarily. For example, 30 to 70% by mass is preferable, 40 to 70% by mass is more preferable, 50 to 65% by mass is further preferable, and 52 to 65% by mass is particularly preferable.
  • the photosensitive resin composition of the present invention contains (e) a surfactant from the viewpoint of improving coatability and suppressing pin unevenness during hot plate drying.
  • the photosensitive resin composition of the present invention has a surface tension of a 0.5 mass% propylene glycol monomethyl ether acetate solution at 23 ° C. (hereinafter, simply referred to as "surface tension") in order to suppress pin unevenness during hot plate drying.
  • a surface active agent (e1) having a value of 23.0 mN / m or less.
  • the surfactant (e1) is not particularly limited as long as the surface tension is 23.0 mN / m or less, but from the viewpoint of suppressing pin unevenness, a silicone-based surfactant and a fluorine-based surfactant are preferable, and a fluorine-based surfactant is preferable.
  • Surfactants are particularly preferred.
  • surfactant (e1) various surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used. Nonionic surfactants are preferred because they are less likely to adversely affect properties.
  • surfactant (e1) examples include F-559 (manufactured by DIC Corporation, surface tension: 22.5 mN / m).
  • the (e) surfactant in the present invention may contain other surfactants in addition to the surfactant (e1) for the purpose of adjusting the coatability.
  • examples of other surfactants include BYK-330 (manufactured by Big Chemie, surface tension: 24.4 mN / m), F-475 (manufactured by DIC, surface tension: 25.4 mN / m), F-554 (manufactured by DIC). DIC, surface tension: 23.3 mN / m).
  • the other surfactant one type may be used, or two or more types may be used in combination in any combination and ratio.
  • the surface tension of the surfactant is measured by a suspension method under the condition of 23 ° C. using a surface tensiometer and a solution prepared by adding 0.5% by mass of the surfactant to a propylene glycol monomethyl ether acetate solution. can do. Further, the d / D method can be used as the analysis method.
  • the content ratio of the surfactant is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass, based on the total solid content of the photosensitive resin composition.
  • the above is more preferable, and 0.15% by mass or more is particularly 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 or less is particularly preferable.
  • Pin unevenness tends to be suppressed by setting the value to the lower limit value or more, and sensitivity tends to improve by setting the value to the upper limit value or less.
  • the above upper and lower limits can be combined arbitrarily. For example, 0.01 to 1.0% by mass is preferable, 0.05 to 0.7% by mass is more preferable, 0.1 to 0.5% by mass is further preferable, and 0.15 to 0.3% by mass is particularly preferable. preferable.
  • the content ratio of the surfactant (e1) is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total solid content of the photosensitive resin composition. , 0.1% by mass or more is more preferable, and 0.15% by mass or more is particularly preferable. Further, it is preferably 1.0% by mass or less, more preferably 0.7% by mass or less, further preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. Especially preferable.
  • By setting the value to the lower limit or higher pin unevenness during hot plate drying tends to be suppressed. Further, the resist sensitivity 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, 0.01 to 1.0% by mass is preferable, 0.05 to 0.7% by mass is more preferable, 0.1 to 0.5% by mass is further preferable, and 0.15 to 0.3% by mass is particularly preferable. preferable.
  • the content ratio of the surfactant (e1) with respect to the total content of the surfactant is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and particularly preferably. Is 90% by mass or more. Moreover, it is 100% by mass or less. By setting the value to the lower limit or higher, pin unevenness during hot plate drying tends to be suppressed.
  • the above upper and lower limits can be combined arbitrarily. For example, 10 to 100% by mass is preferable, 30 to 100% by mass is more preferable, 50 to 100% by mass is further preferable, and 90 to 100% by mass is particularly preferable.
  • a dispersant it is preferable to include a dispersant because it is important to finely disperse the coloring material and stabilize the dispersed state thereof in order to ensure the stability of quality.
  • a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxy group, a phosphoric acid group, a sulfonic acid group, or a base thereof; a primary, secondary or tertiary amino group.
  • a polymer dispersant having a functional group such as a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, or pyrazine; is preferable.
  • Polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, pyrazine; etc. are particularly preferred.
  • a polymer dispersant having a basic functional group By using a polymer dispersant having a basic functional group, the dispersibility can be improved and a high light-shielding property tends to be achieved.
  • polymer dispersant examples include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants consisting of monomers having amino groups and macromonomers, and polyoxyethylene alkyl ethers.
  • examples thereof include dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.
  • dispersant examples include EFKA (registered trademark, manufactured by EFKA), Disperbyk (registered trademark, manufactured by Big Chemie), and Disparon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.) under the trade names.
  • SOLPERSE registered trademark, manufactured by Lubrizol
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow or Floren registered trademark, manufactured by Kyoeisha Chemical Co., Ltd.
  • Azisper registered trademark, manufactured by Ajinomoto Fine Techno Co., Ltd.
  • One type of polymer dispersant may be used alone, or two or more types may be used in combination.
  • the dispersant preferably contains a urethane-based polymer dispersant having a basic functional group and / or an acrylic polymer dispersant. Urethane-based polymer dispersants are particularly preferable in terms of fine wire adhesion. From the viewpoint of dispersibility and storage stability, the dispersant preferably contains a polymer dispersant having a basic functional group and having a polyester and / or a polyether bond.
  • the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 or more, more preferably 1000 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably 30,000 or less. Is. 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.
  • Disperbyk 160 to 167, 182 series all urethane-based
  • Disperbyk2000, 2001 all acrylic-based
  • Disperbyk 167, 182 is mentioned as a particularly preferable polymer dispersant having a basic functional group and having a polyester and / or a polyether bond and having a weight average molecular weight of 30,000 or less.
  • urethane-based polymer dispersant examples include a polyisocyanate compound, a compound having one or two hydroxyl groups in the molecule and a number average molecular weight of 300 to 10,000, and active hydrogen and a tertiary amino group in the same molecule.
  • examples thereof include a dispersed resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting with a compound having a weight average of 1,000 to 200,000.
  • polyisocyanate compound examples include aromatics such as paraphenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and trizine diisocyanate.
  • Diisocyanate Diisocyanate; aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimerate diisocyanate; isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), ⁇ , ⁇ '- Alicyclic diisocyanates such as diisocinatedimethylcyclohexane; aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate; lysine ester triisocyanates, 1,6.
  • aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate,
  • 11-Undecantriisocyanate 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptantriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, etc.
  • Triisocyanates these trimers, water adducts, and polyol adducts thereof.
  • a trimer of organic diisocyanate is preferable, and a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate are particularly preferable. These may be used alone or in combination of two or more.
  • an appropriate trimerization catalyst such as a tertiary amine, a phosphine, an alkoxide, a metal oxide, or a carboxylate is used to prepare an isocyanate group of a polyisocyanate compound.
  • 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. ..
  • polyether glycol As a compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000, for example, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and one-terminal hydroxyl group of these compounds are carbon. Examples thereof include those which are alkoxylated with an alkyl group having a number of 1 to 25, 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 polyether diols obtained by using alkylene oxide alone or in copolymerization, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, and polyoxyoctamethylene. Glycols and mixtures of two or more thereof can be mentioned.
  • polyether ester diol a polyether ester diol obtained by reacting an ether group-containing diol or a mixture with other glycols with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, for example.
  • Poly (polyoxytetramethylene) adipate a polyether ester diol obtained by reacting an ether group-containing diol or a mixture with other glycols with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester glycol with an alkylene oxide, for example.
  • Poly (polyoxytetramethylene) adipate Poly (polyoxytetramethylene) adipate.
  • polyether glycol 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 is preferable.
  • 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, etc.).
  • dicarboxylic acids succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.
  • glycols ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, etc.
  • the polyester glycol polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator is preferable.
  • polycarbonate glycol examples include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
  • polyolefin glycol examples include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. These may be used alone or in combination of two or more.
  • the number average molecular weight of a compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000 is preferably 500 to 6,000, more preferably 1,000 to 4,000.
  • Active hydrogen in a compound having active hydrogen and a tertiary amino group in the same molecule that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom is a functional group such as a hydroxyl group, an amino group or a thiol group.
  • the hydrogen atom in the above is mentioned, and among them, the hydrogen atom of an amino group, particularly a primary amino group is preferable.
  • the tertiary amino group in the compound having an active hydrogen and a tertiary amino group in the same molecule is not particularly limited, but is, for example, an amino group having an alkyl group having 1 to 4 carbon atoms; nitrogen-containing such as an imidazole ring and a triazole ring.
  • a heterocyclic structure can be mentioned.
  • Examples of compounds having active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dipropyl.
  • the nitrogen-containing heterocyclic structure of the tertiary amino group in the compound having active hydrogen and a tertiary amino group in the same molecule includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, and benz.
  • Nitrogen-containing hetero 5-membered ring such as imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, benzothiazol ring; Nitrogen hetero 6-membered ring; As the nitrogen-containing heterocyclic structure, an imidazole ring and a triazole ring are preferable.
  • Examples of the compound having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
  • 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.
  • Compounds having active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl). ) Imidazole and 3-amino-1,2,4-triazole are preferable. These may be used alone or in combination of two or more.
  • the preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 100 parts by mass of the polyisocyanate compound; a compound having one or two hydroxyl groups in the same molecule and having a number average molecular weight of 300 to 10,000. 10 to 200 parts 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;
  • the urethane-based polymer dispersant can be produced according to a known method for producing a polyurethane resin.
  • Solvents that can be used in the production of urethane-based polymer dispersants 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, Hydrocarbons such as toluene, xylene and hexane; some alcohols such as diacetone alcohol, isopropanol, second butanol and tertiary butanol; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; Aprotonic polar solvents such as dimethylformamide, N-methylpyrrolidone,
  • a urethanization reaction catalyst can be used in the production of the urethane-based polymer dispersant.
  • the urethanization reaction catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stanas octoate; iron-based catalysts such as iron acetylacetonate and ferric chloride; triethylamine and tri.
  • tertiary amine-based catalysts such as ethylenediamine;
  • the 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 mass 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 quantification 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, more preferably 5 to 95 mgKOH / g in terms of the amine value after the reaction. ..
  • the amine value is set to the lower limit value or more, the dispersibility tends to be good, and when the amine value is set to the upper limit value or less, the developability tends to be good.
  • the isocyanate group remains in the polymer dispersant, it is preferable to further consume the isocyanate group by using 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 preferably 1,000 to 200,000, more preferably 2,000 to 100,000, and even more preferably 3,000 to 50,000. Further, it is even more preferably 1,000 to 30,000, particularly preferably 2,000 to 30,000, and particularly preferably 3,000 to 30,000. When it is at least the above lower limit value, the dispersibility and dispersion stability tend to be good, and when it is at least the above upper limit value, the solubility tends to be good. In particular, when the weight average molecular weight of the urethane-based polymer dispersant is 30,000 or less, the alkali developability tends to be good even when the pigment concentration is high.
  • Preferred commercially available urethane dispersants include, for example, Disperbyk 167, 182 (Big Chemie).
  • the content ratio of the dispersant is preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 30% by mass, based on the total solid content of the photosensitive resin composition. Is 20% by mass or less, preferably 1% by mass or more, more preferably 3% by mass or more, still 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 preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further, with respect to 100 parts by mass of (d) the coloring material. It is preferably 15 parts by mass or more, preferably 200 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 50 parts by mass or less.
  • the value is equal to or higher than the lower limit, it tends to be easy to secure sufficient dispersibility.
  • 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 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 photosensitive resin composition of the present invention comprises (a) an alkali-soluble resin, (b) a photopolymerizable monomer, (c) a photopolymerization initiator, (e) a surfactant, and various materials used as necessary. However, it may be in a state of being dissolved or dispersed in an organic solvent.
  • an organic solvent a solvent having a boiling point of 100 to 300 ° C. (under pressure 1013.25 [hPa] conditions; hereinafter, the boiling points are all the same) is preferable.
  • a solvent having a boiling point of 120 to 280 ° C. is more preferable.
  • organic solvent examples 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, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, 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-methoxypropionic acid Chain or cyclic esters such as butyl, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-methoxyprop
  • Halogenated hydrocarbons such as butyl chloride, amilk chloride; Etheretones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile.
  • solvents examples include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, and Sokal 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).
  • the solvent may be used alone or in combination of two or more.
  • an organic solvent having a boiling point of 100 to 250 ° C. is preferable.
  • An organic solvent having a boiling point of 120 to 230 ° C. is more preferable.
  • Glycol alkyl ether acetates are preferable because they have a good balance of coatability, surface tension and the like, and the solubility of each component of the photosensitive resin composition is relatively high.
  • Glycol alkyl ether acetates may be used alone or in combination with other organic solvents.
  • Glycol monoalkyl ethers are preferable as other organic solvents that may be used in combination.
  • Propylene glycol monomethyl ether is more preferred 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 pigment 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 mixture 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”) may be used in combination.
  • high boiling point solvent an 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 pigment in the composition from being destroyed by rapid drying. For example, it has 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, diethylene glycol monoethyl ether acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, and 1,3-butanediol diacetate are highly effective when used in combination.
  • 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 drying temperature of the composition By setting it to the above lower limit value or more, for example, it tends to be possible to suppress the precipitation and solidification of coloring materials and the like at the tip of the slit nozzle to cause foreign matter defects, and by setting it to the above upper limit value or less, the drying temperature of the composition. There is a tendency that problems such as poor tact 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 the total solid content in the photosensitive resin composition is preferable from the viewpoint of ease of application and viscosity stability. 5% by mass or more, 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, particularly preferably 20. It is less than mass%.
  • the above upper and lower limits can be combined arbitrarily. For example, 5 to 40% by mass is preferable, 5 to 30% by mass is more preferable, 8 to 25% by mass is further preferable, and 10 to 20% by mass is particularly preferable.
  • thiols for example, thiols, adhesion improvers, pigment derivatives, development improvers, ultraviolet absorbers, and antioxidants can be appropriately added to the photosensitive resin composition of the present invention.
  • the photosensitive resin composition of 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 trimethylolpropanetristhioglycolate.
  • Butanediol Bisthiopropionate Trimethylol Propane Tristhiopropionate, Trimethylol Propane Tristhio Glycolate, Pentaerythritol Tetrakissthiopropionate, Pentaerythritol Tetrakissthioglycolate, Trishydroxyethyl Tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate) (PGMB), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane (Product name: Karenz MT BD1, manufactured by Showa Denko Co., Ltd.), Butanediol Trimethylol Propanthris (3-mercaptobutyrate), Pentaerythritol tetrakis (3-mercaptobutyrate) (Product name: Karenz MT PE
  • thiols polyfunctional thiols such as PGMB, TPMB, TPMIB, Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are preferable, Karenz MT BD1, Karenz MT PE1 and Karenz MT NR1 are more preferable, and Karenz MT PE1 is particularly preferable. preferable.
  • the content ratio of the thiols 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 of the present invention. Is 0.5% by mass or more, preferably 10% by mass or less, and more 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 good.
  • 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.
  • 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.
  • the silane coupling agent include KBM-402, KBM-403, KBM-502, KBM-5103, KBE-9007, X-12-1048, X-12-1050 (manufactured by Shinetsu Silicone Co., Ltd.), Z-6040. , Z-6043, 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.
  • (meth) acryloyloxy group-containing phosphates are preferable, and (meth) acryloyloxy group-containing phosphates represented by the following general formulas (g1), (g2), and (g3) are preferable.
  • R 51 independently represents a hydrogen atom or a methyl group
  • m are independently 1, 2 respectively. Or it is 3.
  • adhesion improvers examples include TEGO * Add Bond LTH (manufactured by Evonik).
  • TEGO * Add Bond LTH manufactured by Evonik
  • phosphoric acid-based adhesion improver and other adhesion improvers one type may be used alone or two or more types may be used in combination.
  • the content ratio of the adhesion improver is not particularly limited, but is preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition, and 0. 1% by mass or more is more preferable, 0.5% by mass or more is further preferable, 5.0% by mass or less is preferable, 3.0% by mass or less is more preferable, and 2.0% by mass or less is further preferable. 5.5% 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 5.0% by mass is preferable, 0.01 to 3.0% by mass is more preferable, 0.1 to 2.0% by mass is further preferable, and 0.5 to 1.5% by mass is preferable. Especially preferable.
  • the photosensitive resin composition of 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. Examples include systems and dioxazine-based derivatives.
  • a phthalocyanine-based derivative and a quinophthalone-based derivative are preferable.
  • a substituent such as a sulfonic acid group, a sulfonamide group, a quaternary salt of a sulfonamide group, a phthalimidemethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxy group or an amide group is directly on the pigment skeleton or an alkyl group. Examples thereof include derivatives bonded via an aryl group, a heterocyclic group and the like.
  • the substituent of the pigment derivative is preferably a sulfonic acid group.
  • one pigment skeleton may be substituted with a plurality of substituents.
  • the pigment derivative examples include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinophthalone, a sulfonic acid derivative of anthraquinone, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of diketopyrrolopyrrole, and a sulfonic acid derivative of dioxazine. These may be used alone or in combination of two or more.
  • the content ratio of the pigment derivative is not particularly limited, but is preferably 0.1% by mass or more, preferably 0.5% by mass, based on the total solid content of the photosensitive resin composition.
  • 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 of 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 film thickness of the coating film on which the photosensitive resin composition of the present invention is cured is preferably 4.0 or more, more preferably 4.1 or more, still more preferably 4.2 or more. Further, it is preferably 6.0 or less.
  • the optical density means a transmission optical density in which the spectral sensitivity characteristic of the light receiving portion is indicated by ISO visual density in the ISO 5-3 standard.
  • the light source the A light source specified by the CIE (Commission Internationale de l'Eclairage) is used.
  • CIE Commission Internationale de l'Eclairage
  • X-Rite 361T (V) manufactured by Sakata Inx Corporation can be mentioned.
  • the photosensitive resin composition of the present invention is produced by a conventional method.
  • the coloring material is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the (d) coloring material is made into fine particles by the dispersion treatment, the coating characteristics of the photosensitive resin composition are improved.
  • a black color material is used as the color material, it contributes to the improvement of the light-shielding ability.
  • the dispersion treatment it is preferable to carry out the dispersion treatment in a system in which (d) a coloring material, a solvent, and a dispersant as necessary, and (a) a part or all of the alkali-soluble resin are used in combination (hereinafter, a mixture to be subjected to the dispersion treatment, and a mixture).
  • the mixture obtained by the dispersion treatment may be referred to as "ink” or "pigment dispersion”).
  • a polymer dispersant as the dispersant because the obtained ink and the photosensitive resin composition are excellent in dispersion stability and thickening with time is suppressed.
  • the highly reactive components may be denatured due to the heat generated during the dispersion treatment. Therefore, in that case, it is preferable to carry out the dispersion treatment in a system containing a polymer dispersant.
  • the 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 temperature is preferably in the range of 0 ° C to 100 ° C, more preferably in the range of room temperature to 80 ° C.
  • the dispersion time will be adjusted as appropriate because the appropriate time will vary depending on the composition of the liquid and the size of the dispersion treatment device.
  • the guideline for dispersion is to control the gloss of the ink so that the 20-degree mirror gloss (JIS Z8741) of the photosensitive resin composition is in the range of 100 to 200.
  • the dispersion treatment is not sufficient and rough pigment (coloring material) particles often remain, resulting in insufficient developability, adhesion, resolution and the like. there is a possibility.
  • 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 ink obtained by the dispersion treatment and other components contained in the photosensitive resin composition are mixed to obtain a uniform solution.
  • the cured product of the present invention can be 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 black matrix of the present invention comprises the cured product of the present invention.
  • the black matrix of the present invention will be described according to the production method using the photosensitive resin composition of the present invention.
  • 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 an unsaturated polyester resin or a poly (meth) acrylic resin, or 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 the TFT array.
  • the thickness of the transparent substrate is preferably 0.05 to 10 mm, more preferably 0.1 to 7 mm.
  • the film thickness is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m.
  • the photosensitive resin composition of the present invention is applied on a transparent substrate, and a photomask is placed on a dried sample.
  • a black matrix is formed by image exposure, development, and heat curing or photocuring as required through a photomask.
  • the thickness of the coating film is preferably 0.2 to 10 ⁇ m, more preferably 0.5 to 6 ⁇ m, and even more preferably 1 to 4 ⁇ m as the film thickness after drying.
  • (3-2) Drying of coating film Drying of the coating film after applying the photosensitive resin composition to the substrate is performed by a vacuum drying method using a vacuum drying device and heating using a hot plate, an IR oven, or a convection oven.
  • the drying method is preferable. In the case of the heat drying method using a hot plate, it may be supported by a pin from the back surface of the substrate.
  • the conditions for heat drying can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
  • the drying time is preferably selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., more 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 higher the drying temperature the better the adhesiveness of the coating film to the transparent substrate. If the drying temperature is not too high, the decomposition of the alkali-soluble resin can be suppressed, and development defects can be suppressed without inducing thermal polymerization. Further, if the drying proceeds uniformly, the film thickness becomes uniform and the occurrence of unevenness can be suppressed.
  • 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.
  • 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 lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, and carbon arcs.
  • 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 applied.
  • an organic solvent or an aqueous solution containing a surfactant and an alkaline compound is applied.
  • an image can be formed and produced on the substrate.
  • the aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.
  • alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate.
  • Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine.
  • 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 alkylbetaines and amino acids.
  • 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 10 to 50 ° C., preferably 15 to 45 ° C., particularly preferably 20 to 40 ° C., and a dip development method, a spray development method, a brush development method, or an ultrasonic development method. It can be done by such a method.
  • 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 preferably 0.5 to 5 ⁇ m, more preferably 0.8 to 4 ⁇ m.
  • the optical density (OD) per 1 ⁇ m of the film thickness of the black matrix of the present invention is preferably 4.0 or more, more preferably 4.1 or more, still more preferably 4.2 or more. Further, it is preferably 6.0 or less. By setting the value to the lower limit or more, there is a tendency that sufficient light-shielding property can be ensured.
  • the above upper and lower limits can be combined arbitrarily. For example, 4.0 to 6.0 is preferable, 4.1 to 6.0 is more preferable, and 4.2 to 6.0 is even more preferable.
  • 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 of the present invention can also be used as a resist for a colored spacer in addition to the black matrix.
  • the spacer 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.
  • 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 image display device of the present invention has a black matrix of the present invention, a cured product of the present invention, or a cured product obtained by curing the photosensitive resin composition of the present invention.
  • the image display device is not particularly limited as long as it is a device that displays an image or a moving image. Examples of the image display device include a liquid crystal display device and an organic EL display.
  • the image display device of the present invention may be a liquid crystal display device and has the black matrix of the present invention.
  • the formation order and formation position of the color pixels and the black matrix are not particularly limited.
  • 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 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 preferably 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 preferably 1 ⁇ 10 ⁇ 2 to 1 ⁇ 10 -7 Pa, but more 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 preferably 30 to 100 ° C, more preferably 50 to 90 ° C.
  • the warming retention at the time of depressurization is preferably 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 injection port of the liquid crystal cell into which the liquid crystal is injected by curing the UV curable resin.
  • 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.
  • the image display device of the present invention may be an organic EL display and has the black matrix of the present invention.
  • the organic EL display having the black matrix of the present invention is produced, for example, as shown in FIG. 1, a pattern formed by the photosensitive resin composition (that is, pixels 20 and adjacent pixels) is formed on the transparent support substrate 10. A color filter in which a resin black matrix (not shown) provided between 20 is formed is produced, and an organic illuminant 500 is laminated on the color filter via an organic protective layer 30 and an inorganic oxide film 40. Thereby, the organic EL element 100 can be manufactured.
  • the resin black matrix is 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 a 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, Luminescent, Shizushi Tokito, Chihaya Adachi, Hideyuki Murata), etc. , An organic EL display can be manufactured.
  • the black matrix of the present invention can be applied to both a passive drive type organic EL display and an active drive type organic EL display.
  • TMP trimethylolpropane
  • BPDA biphenyltetracarboxylic acid dianhydride
  • THPA tetrahydrophthalic acid anhydride
  • Alkali-soluble resin-II Resin described in Synthesis Example 1
  • Alkali-soluble resin-III resin described in Synthesis Example 2 ⁇ photopolymerizable monomer>
  • DPHA "KAYARAD DPHA” (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd. It does not have a partial structure represented by the chemical formula (b5).
  • DPCA-20 "KAYARAD DPCA-20” (polyfunctional acrylate) manufactured by Nippon Kayaku Co., Ltd.
  • DPCA-20 has the following structure and corresponds to a photopolymerizable monomer (b6) having a partial structure represented by the chemical formula (b5).
  • Table 1 shows the surface tension values of propylene glycol monomethyl ether acetate (PGMEA) to which 0.5% by mass of the above surfactant was added at 23 ° C.
  • the surface tension value was measured by the suspension method using the DropMaster DMo-601 manufactured by Kyowa Surface Chemistry, and analyzed by the d / D method. In addition, 3.5 ⁇ L droplets were used for the measurement.
  • dispersion-I dispersion-II
  • This carbon black ink (dispersion liquid-I, dispersion liquid-II) had good dispersibility without thickening.
  • the photosensitive resin composition is applied onto a glass substrate with a spin coater so that the film thickness after heat curing is 1.2 ⁇ m, dried under reduced pressure at 100 Pa for 60 seconds, and then dried on a hot plate at 100 ° C. for 120 seconds. did.
  • the obtained coating film was subjected to full-scale exposure treatment so that the exposure amount was 40 mJ / cm 2 using ultraviolet rays having an intensity of 60 mW / cm 2 at a wavelength of 365 nm without using a photomask.
  • the optical density (OD) of the obtained substrate is measured with a transmission densitometer (361T (V) manufactured by X-Rite), and the film thickness of the cured film of the photosensitive resin composition is measured with a scanning white interference microscope (Hitachi High Technology). It was measured by VS1530) manufactured by the company.
  • the optical density (unit / ⁇ m) per unit film thickness (1.0 ⁇ m) was calculated from the optical density (OD) and the film thickness, and is shown in Table 3.
  • the OD value is a numerical value indicating the light-shielding ability, and the larger the value is, the higher the light-shielding property is.
  • a substrate for evaluating fine line adhesion was prepared in the same manner as the substrate for optical density measurement, except that a photomask having a line width opening of 1 ⁇ m to 20 ⁇ m in 1 ⁇ m increments was used as the photomask.
  • the linear pattern of the obtained substrate was observed with an optical microscope (Eclipse L200ND manufactured by Nikon Corporation), the mask aperture size of the smallest pattern remaining without chipping was measured as fine line adhesion, and the obtained results were evaluated as follows. did.
  • a substrate for measuring adhesion stress was produced in the same manner as the substrate for measuring optical density.
  • a sample prepared by joining an aluminum stud pin (manufactured by Quad) to the cured film side of the photosensitive resin composition of the obtained substrate using a sealing agent (XN-21-S manufactured by Mitsui Kagaku Co., Ltd.) is pulled.
  • a testing machine Romulus manufactured by Quad
  • the stud pin was pulled at a speed of 2.0 kg / s to perform a tensile test, and when the cured film of the photosensitive resin composition and the glass substrate were broken.
  • the adhesion stress was calculated from the breaking strength and the adhesive area by the following formula.
  • Adhesion stress (kgf / cm 2 ) breaking strength (kgf) / adhesive area (cm 2 )
  • Adhesion stress was evaluated as follows. A: Adhesion stress ⁇ 175kgf / cm 2 B: 175kgf / cm 2 > Adhesion stress ⁇ 150kgf / cm 2 C: 150kgf / cm 2 > Adhesion stress
  • the photosensitive resin composition was applied onto a glass substrate with a spin coater so that the film thickness after heat curing was 1.2 ⁇ m, and dried under reduced pressure at 100 Pa for 60 seconds to obtain a sample (glass substrate / coating film).
  • a sample is placed on a columnar metal pin (diameter 1 cm, height 1 cm) placed on a hot plate so that the glass substrate side is in contact with the metal pin, dried at a hot plate temperature of 100 ° C. for 120 seconds, and then metal.
  • the photosensitive resin composition of Example 1 has good fine wire adhesion and adhesion stress with the substrate even when the optical density per unit film thickness is 4.0 or more. Surprisingly, it can be seen that the pin unevenness during hot plate drying is also good.
  • Example 1 By comparing Example 1 and Comparative Examples 3 and 4, by containing a photopolymerizable monomer (b6) containing a partial structure represented by the general formula (b5) in addition to the alkali-soluble resin having a cardo skeleton. It can be seen that both fine wire adhesion and adhesion stress are compatible. This is because the inclusion of the alkali-soluble resin (a1) having a highly hydrophobic cardo skeleton suppresses the penetration of the developing solution during the developing process and improves the fine line adhesion, while the cardo skeleton has an aromatic ring. Since the structure has an integrated high rigidity, the film tends to warp, which causes a decrease in the adhesion stress of the substrate. However, by containing the photopolymerizable monomer (b6) containing a flexible alkylene chain, the warp is likely to occur. Is relaxed, and it is considered that the decrease in adhesion stress is suppressed.
  • Example 1 by comparing Example 1 and Comparative Examples 1 to 4, among the alkali-soluble resin (a1) having a cardo skeleton, the photopolymerizable monomer (b6) having a partial structure represented by the general formula (b5), and PGMEA. It can be seen that the pin unevenness evaluation during hot plate drying is particularly good when the surfactant (e1) having a surface tension of 23.0 mN / m or less when 0.5% by mass is added is used in combination.
  • the photosensitive resin composition of Example 1 contains a resin having a cardo skeleton in which an aromatic ring having a high affinity with carbon black is accumulated, thereby preventing carbon black from agglomerating even when the hot plate is dried, and further.
  • the photosensitive resin composition of Example 1 sufficiently heat-flows even in a portion where the metal pin having a relatively low temperature does not come into contact with the hot plate, and heat flows with the portion in contact with the metal pin having a high temperature. It is considered that when the difference in sex becomes small, the difference in surface roughness becomes small, and as a result, the occurrence of pin unevenness is suppressed.
  • Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

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