WO2022039034A1 - Colored photosensitive resin composition, cured object, display device, and method for producing cured object - Google Patents

Colored photosensitive resin composition, cured object, display device, and method for producing cured object Download PDF

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Publication number
WO2022039034A1
WO2022039034A1 PCT/JP2021/029076 JP2021029076W WO2022039034A1 WO 2022039034 A1 WO2022039034 A1 WO 2022039034A1 JP 2021029076 W JP2021029076 W JP 2021029076W WO 2022039034 A1 WO2022039034 A1 WO 2022039034A1
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Prior art keywords
resin composition
photosensitive resin
dye
colored photosensitive
acid
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PCT/JP2021/029076
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French (fr)
Japanese (ja)
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西岡拓紀
小森悠佑
三好一登
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東レ株式会社
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Priority to KR1020227040798A priority Critical patent/KR20230051765A/en
Priority to JP2021546701A priority patent/JPWO2022039034A1/ja
Priority to CN202180056116.5A priority patent/CN116034318A/en
Publication of WO2022039034A1 publication Critical patent/WO2022039034A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to a colored photosensitive resin composition, a cured product using the same, a display device, and a method for producing the cured product. More specifically, a surface protective film of a semiconductor element, an interlayer insulating film, an electroluminescence (hereinafter referred to as EL) element pixel dividing layer, and a thin film transistor for driving a display device using an organic EL element. : Hereinafter referred to as TFT.) Suitable for substrate flattening film, circuit board wiring protective insulating film, on-chip microlens of solid-state image pickup element, flattening film for various displays and solid-state image pickup elements, solder resist for circuit board, etc. Further, the present invention relates to a cured product and a colored photosensitive resin composition for forming the cured product.
  • the cured product obtained by curing a composition containing polyimide or polybenzoxazole is widely used as an insulating film, a protective film, a flattening film, etc. of semiconductor devices and display devices.
  • a display device for example, in applications such as a pixel division layer of an organic EL display and a black matrix of a liquid crystal display, it is required to reduce the light transmission rate of the cured product in order to improve the contrast. ing.
  • it is transmitted through the pixel dividing layer of the organic EL display and the flattening film provided on the TFT substrate of the organic EL display. It is required to lower the rate.
  • Patent Document 1 a method of adding a quinonediazide compound and a black pigment to an alkali-soluble resin composed of a novolak resin and / or a vinyl polymer.
  • Patent Document 2 a method of adding a photosensitizer and a black pigment to a soluble polyimide (see Patent Document 2), and a method of adding a quinonediazide compound, an alkaline developer and a dye soluble in both an organic solvent to an alkali-soluble resin.
  • Patent Document 4 a method of adding a black oil-soluble dye to a photosensitive resin (see Patent Document 4), and at least one selected from a quinonediazide compound and a dye, an inorganic pigment, and an organic pigment esterified to an alkali-soluble heat-resistant resin.
  • Patent Document 5 a method of adding a colorant (see Patent Document 5), and the like.
  • Japanese Unexamined Patent Publication No. 6-230215 Japanese Patent Application Laid-Open No. 2003-119381 Japanese Unexamined Patent Publication No. 7-261015 Japanese Unexamined Patent Publication No. 10-254129 Japanese Unexamined Patent Publication No. 2004-145320
  • the present invention is a colored photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant is a (C1) acid dye. It is a colored photosensitive resin composition containing a salt-forming compound composed of a basic dye and a basic dye.
  • pattern processing is possible while achieving both the characteristics of residual film ratio, opening residue, and blackness.
  • the present invention is a colored photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant is a (C1) acid dye. It is a colored photosensitive resin composition containing a salt-forming compound composed of a basic dye and a basic dye.
  • the present invention will be described in detail.
  • the colored photosensitive resin composition of the present invention contains (A) an alkali-soluble resin.
  • the alkali-soluble resin means a resin having a dissolution rate of 50 nm / min or more as defined below. Specifically, a solution in which a resin is dissolved in ⁇ -butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebake film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m, and the prebake film is formed by 23 ⁇ .
  • a resin having a dissolution rate of 50 nm / min or more obtained from a decrease in film thickness when immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 1 ° C. for 1 minute and then rinsed with pure water.
  • the alkali-soluble resin preferably has an acidic group in the structural unit of the resin and / or at the end of the main chain thereof in order to impart alkali solubility.
  • Preferred acidic groups include carboxyl groups, hydroxyl groups, sulfonic acid groups, thiol groups and the like.
  • the alkali-soluble resin examples include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, phenol resin, a polymer composed of a radically polymerizable monomer having an alkali-soluble group, a siloxane polymer, and a cyclic olefin. Examples include polymers and cardo resins.
  • the alkali-soluble resin may contain two or more of these resins.
  • the alkali-soluble resin (A) preferably contains a resin having high heat resistance.
  • the alkali-soluble resin (A) has a temperature of 200 ° C. or higher after heat treatment. It is preferable to contain a substance having a small amount of outgas under high temperature.
  • the alkali-soluble resin (A) preferably contains at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and copolymers thereof. ..
  • polyimide it is not particularly limited as long as it has an imide ring
  • polybenzoxazole it is not particularly limited as long as it has a benzoxazole ring
  • the polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring by dehydration closing
  • the polybenzoxazole precursor is also a polybenzo having a benzoxazole ring by dehydration closing.
  • it is not particularly limited.
  • (A) More preferably used as the alkali-soluble resin include polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.
  • Polyimide has a structural unit represented by the general formula (1).
  • R 1 represents a 4- to 10-valent organic group having 5 to 40 carbon atoms
  • R 2 represents a 2- to 10-valent organic group having 5 to 40 carbon atoms
  • R 3 and R 4 independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3).
  • p represents an integer of 0 to 6
  • q represents an integer of 0 to 8
  • R 5 to R 7 independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 to 6 carbon atoms. Represents 15 aryl groups.
  • the above-mentioned alkyl group, acyl group and aryl group may be an unsubstituted or substituted product.
  • the polyimide precursor has a structural unit represented by the general formula (4).
  • R 8 represents a 4- to 10-valent organic group having 5 to 40 carbon atoms
  • R 9 represents a 2- to 10-valent organic group having 5 to 40 carbon atoms
  • R 10 represents a substituent represented by the general formula (2) or the general formula (3)
  • R 11 represents a hydroxyl group, a sulfonic acid group, and a thiol group
  • R 12 represents a hydroxyl group, a sulfonic acid group, a thiol group, or a thiol group.
  • r represents an integer of 2 to 8
  • s represents an integer of 0 to 6
  • t represents an integer of 0 to 8, and 2 ⁇ r + s ⁇ 8.
  • Polybenzoxazole has a structural unit represented by the general formula (5).
  • R 13 represents a 2- to 8-valent organic group having 5 to 40 carbon atoms
  • R 14 represents a 4- to 10-valent organic group having an aromatic structure and 5 to 40 carbon atoms
  • R 15 and R 16 independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3).
  • u represents an integer of 0 to 8
  • v represents an integer of 0 to 6
  • the polybenzoxazole precursor has a structural unit represented by the general formula (6).
  • R 17 represents a 4- to 10-valent organic group having an aromatic structure and having 5 to 40 carbon atoms
  • R 18 represents a 2- to 10-valent organic group having 5 to 40 carbon atoms
  • R 19 represents a sulfonic acid group, a thiol group or a substituent represented by the general formula (2) or the general formula (3)
  • R 20 is a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group or a general formula (2).
  • it represents a substituent represented by the general formula (3).
  • w represents an integer of 2 to 8
  • x represents an integer of 0 to 8
  • y represents an integer of 0 to 6, and 2 ⁇ w + y ⁇ 8.
  • One or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymers are the above general formulas (1), general formulas (4) and general formulas (5).
  • the structural unit represented by the general formula (6) is preferably 5 to 100,000.
  • one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymers are the above general formulas (1), general formulas (4) and general formulas.
  • other structural units may be included.
  • At least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and a copolymer thereof is the above general formula (1), general formula (4), general. It is preferable to have 50 mol% or more of the total number of structural units, and more preferably 70 mol% or more, of the structural units represented by the formula (5) or the general formula (6).
  • R 1- (R 3 ) p in the general formula (1) and (R 10 ) r -R 8- (R 11 ) s in the general formula (4) represent residues of the tetracarboxylic acid or its derivative. .. Residues of the tetracarboxylic acid derivative include residues of tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride or tetracarboxylic acid active diester.
  • Residues of tetracarboxylic acid and its derivatives include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2'.
  • R 21 represents an oxygen atom, C (CF 3 ) 2 , or C (CH 3 ) 2 .
  • R 22 and R 23 independently represent a hydrogen atom or a hydroxyl group, respectively.
  • R 13- (R 15 ) u in the general formula (5) and R 17- (R 19 ) x in the general formula (6) represent residues of a dicarboxylic acid or a derivative thereof.
  • the residue of the dicarboxylic acid derivative include residues of a dicarboxylic acid anhydride, a dicarboxylic acid acid compound, a dicarboxylic acid active ester, a tricarboxylic acid anhydride, a tricarboxylic acid acid compound, a tricarboxylic acid active ester, and a diformyl compound.
  • Examples of the residue of the dicarboxylic acid and its derivative include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenone dicarboxylic acid, triphenyldicarboxylic acid, and the like, or dicarboxylic acids thereof.
  • Examples thereof include anhydrides, dicarboxylic acid salts, residues of dicarboxylic acid active esters, and the like.
  • the residues of the tricarboxylic acid and its derivatives include trimellitic acid, trimethic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., or the residues of their tricarboxylic acid anhydrides, tricarboxylic acid salts, and tricarboxylic acid active esters. And so on.
  • R 2- (R 4 ) q in the general formula (1) and R 9- (R 12 ) t in the general formula (4) represent residues of diamines or derivatives thereof.
  • R 14- (R 16 ) v in the general formula (5) and (OH) w -R 18- (R 20 ) y in the general formula (6) are bisaminophenol compounds or derivative residues thereof. show.
  • the residue of the bis-aminophenol compound derivative include a diisocyanate compound and a trimethylsilylated diamine.
  • the residues of the bisaminophenol compound and its derivatives include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 1,4-bis.
  • (4-Aminophenoxy) Benzene benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis ⁇ 4- (4- (4-) Aminophenoxy) phenyl ⁇ ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl , 3,3', 4,4'-Tetramethyl-4,4'-diaminobiphenyl, 2,2'-d
  • R 21 represents an oxygen atom, C (CF 3 ) 2 , or C (CH 3 ) 2 .
  • R 22 to R 25 independently represent a hydrogen atom or a hydroxyl group, respectively.
  • an alkali-soluble resin having an acidic group at the end of the main chain can be obtained. ..
  • Preferred examples of monoamines having such acidic groups are 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino.
  • Examples thereof include -4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.
  • acid anhydrides, acid chlorides, and monocarboxylic acids include acids such as phthalic anhydride, maleic anhydride, nagic acid anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride.
  • Anhydrides, monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, monoacid chloride compounds in which these carboxyl groups are acid chlorides, monoacid chloride compounds and N. Examples thereof include active ester compounds obtained by reaction with -hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboxyimide. Two or more of these may be used.
  • the (A) alkali-soluble resin used in the colored photosensitive resin composition is synthesized by a known method.
  • a polyimide precursor for example, polyamic acid or polyamic acid ester
  • a production method for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, or a method of reacting a tetracarboxylic acid dianhydride with an alcohol to obtain a diester is obtained.
  • polyimide it can be obtained, for example, by dehydrating and closing the polyamic acid or polyamic acid ester obtained by the above method by heating or chemical treatment with an acid or a base.
  • a polybenzoxazole precursor for example, polyhydroxyamide
  • it can be obtained by subjecting a bisaminophenol compound to a dicarboxylic acid in a condensation reaction.
  • a solution of dichloride is dropped.
  • polybenzoxazole for example, it can be obtained by dehydrating and ring-closing the polyhydroxyamide obtained by the above-mentioned method by heating or chemical treatment with an acid or a base.
  • the colored photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • a photoacid generator examples include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like, and quinonediazide compounds are preferable.
  • the quinone-diazide compound includes a polyhydroxy compound or a polyamino compound with an ester bond of quinone-diazide sulfonic acid, a polyhydroxy compound with a sulfonic acid of quinone-diazide bonded with a sulfonamide, and a polyhydroxypolyamino compound with an ester bond of quinone-diazide sulfonic acid. / Or a sulfonamide-bonded substance or the like.
  • the quinone diazide compound substituted in an amount of 50 mol% or more the affinity of the quinone diazide compound with respect to the alkaline aqueous solution is lowered, the solubility of the unexposed resin composition in the alkaline aqueous solution is greatly lowered, and the quinone diazide is exposed by exposure.
  • the sulfonyl group is changed to indencarboxylic acid, and a large dissolution rate of the resin composition of the exposed portion in the alkaline aqueous solution can be obtained. As a result, the dissolution rate ratio of the exposed portion and the unexposed portion of the composition is increased to be high. You can get the pattern at the resolution.
  • a quinone diazide compound By using such a quinone diazide compound, a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general mercury lamp can be obtained.
  • the photoacid generator may be used alone or in combination of two or more, and a highly sensitive photosensitive resin composition can be obtained.
  • the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
  • the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure and all-wavelength exposure.
  • the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
  • a naphthoquinone diazidosulfonyl ester compound in which a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group are used in combination in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound. Can also be used together.
  • the molecular weight of the photoacid generator is preferably 300 or more, more preferably 350 or more, preferably 3000 or less, more preferably 3000 or less, from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the cured product obtained by heat treatment. Is 1500 or less.
  • the content of the (B) photoacid generator is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 100 parts by mass or less, based on 100 parts by mass of the (A) alkali-soluble resin. It is preferably 80 parts by mass or less. If it is 1 to 100 parts by mass, it is possible to impart photosensitivity while maintaining the heat resistance, chemical resistance and mechanical properties of the cured product after heat treatment.
  • the colored photosensitive resin composition of the present invention contains (C) a colorant, and the (C) colorant contains a salt-forming compound composed of (C1) an acid dye and a basic dye.
  • the salt-forming compound composed of an acid dye and a basic dye is a compound obtained by reacting an acid dye with a basic dye. It is a compound obtained by a chemical (salt-forming) reaction between an acidic dye having an anionic dye ion and a basic dye having a cationic dye ion, and is chemically stable.
  • the colored photosensitive resin composition of the present invention does not contain an acid dye and a basic dye individually, but contains (C1) a salt-forming compound composed of an acid dye and a basic dye.
  • the inclusion as a salt-forming compound is preferable because it does not contain the counter ions of the acid dye and the basic dye as compared with the case where the acid dye and the basic dye are contained alone.
  • the acid dye is a compound having an acidic substituent such as a sulfo group or a carboxy group in the molecule, or an anionic water-soluble dye which is a salt thereof.
  • the acid dye includes not only acid dyes in a narrow sense but also those directly classified as dyes if they have an acidic substituent such as a sulfo group or a carboxy group.
  • Examples of the acid dye include C.I. I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; C.I. I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C.I. I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; C.I. I. Acid Brown 2, 4, 13, 248; C.I. I. Acid Violet 11, 56, 58; C.I. I.
  • Azo-based acid dyes such as acid blue 92, 102, 113, 117; C. I. Quinoline acid dyes such as Acid Yellow 2, 3, 5; C. I. Xanthene acid dyes such as Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289; C. I. Acid Red 82, 92; C.I. I. Acid Violet 41, 42, 43; C.I. I. Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127: 1, 129, 145, 167, 230; C.I. I. Anthraquinone-based acid dyes such as Acid Green 25 and 27; C. I. Acid Violet 17, 49; C.I. I.
  • the acid dye preferably contains a xanthene-based acid dye and / or a triarylmethane-based acid dye in that the opening residue can be reduced.
  • a xanthene-based acid dye such as Acid Red 50, 52, 289.
  • the xanthene-based acid dye can increase the blackness (OD value) of the cured product, and thus C.I. I. It is more preferable to contain Acid Red 52.
  • the acid dye preferably has a solubility in a 2.38% by mass tetramethylammonium hydroxide aqueous solution as a sodium salt of 4% by mass or more and 9% by mass or less.
  • a salt-forming compound using an acid dye satisfying this can increase the residual film ratio and reduce the amount of opening residue.
  • the acid dye when the acid dye is a salt other than the sodium salt, the acid dye can be made into a sodium salt by using a sodium type cation exchange resin or the like.
  • the solubility in a 2.38 mass% tetramethylammonium hydroxide aqueous solution can be determined from the limit amount of the acid dye sodium salt added little by little to the aqueous solution at 25 ° C. and dissolved by stirring. can.
  • the number of acidic groups in the anion portion of the acid dye is preferably 2 or more and 6 or less per 1000 molecular weight of the anion portion in the acid dye.
  • a salt-forming compound using an acid dye satisfying this can increase the residual film ratio and reduce the amount of opening residue.
  • the molecular weight of the anion portion can be calculated from the structural formula.
  • the basic dye is a compound having a basic substituent such as an amino group or an imino group in the molecule, or a cationic water-soluble dye which is a salt thereof.
  • Methine-based basic dyes such as Basic Violet 16, 39; C. I. Anthraquinone-based basic dyes such as Basic Blue 22, 35, 45, 47; C. I. Basic Violet 1, 2, 3, 4, 13, 14, 23; C.I. I. Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24, 26; C.I. I. Examples thereof include triarylmethane-based basic dyes such as Basic Greens 1 and 4.
  • the basic dye preferably contains a xanthene-based basic dye and / or a triarylmethane-based basic dye in that the blackness (OD value) of the cured product can be increased, and is preferably a triarylmethane-based basic dye. It is more preferably a dye.
  • Triarylmethane-based basic dyes can increase the blackness (OD value) of the cured product, and thus C.I. I. Basic Blue 7 and / or C.I. I. It is more preferable to contain Basic Blue 26.
  • the acid dye preferably contains a xanthene-based acid dye and / or a triarylmethane-based acid dye.
  • the basic dye preferably contains a xanthene-based basic dye and / or a triarylmethane-based basic dye.
  • Both the acid dye and the basic dye preferably contain a xanthene-based basic dye and / or a triarylmethane-based basic dye. That is, it is preferable that the acid dye and / or the basic dye contains a xanthene dye and / or a triarylmethane dye.
  • the basic dye preferably has a cation portion having a molecular weight of 300 or more and 700 or less.
  • a salt-forming compound using a basic dye satisfying this can increase the residual film ratio and reduce the opening residue.
  • the molecular weight of the cation part can be calculated from the structural formula.
  • the salt-forming compound composed of an acidic dye and a basic dye has one or more acidic dyes and one or more basics having a maximum absorption wavelength of 500 nm or more and 700 nm or less in the region of 350 nm or more and 700 nm or less. It is preferable to contain a salt-forming compound composed of a dye.
  • ⁇ a is in the range of 500 nm or more and less than 580 nm.
  • ⁇ a is present in any of the ranges of 580 nm or more and 700 nm or less
  • ⁇ b is 500 nm or more and less than 580 nm . It is preferably present in any of the ranges.
  • the absolute value of the difference between ⁇ a and ⁇ b is more preferably 40 nm or more and 150 nm or less.
  • a salt-forming compound using an acid dye and a basic dye that satisfy each of these can increase the blackness (OD value) of the cured product.
  • the salt-forming compound of the acid dye and the basic dye can be synthesized by a known method. For example, when an aqueous solution of an acid dye and an aqueous solution of a basic dye are prepared and mixed, a salt-forming compound of the acid dye and the basic dye is produced.
  • the salt-forming compound can be obtained by recovering this by filtration.
  • the obtained salt-forming compound is preferably dried at about 60 to 70 ° C.
  • the colored photosensitive resin composition of the present invention preferably further contains (C2) a nonionic dye and / or (C3) a pigment as the (C) colorant. Above all, it is preferable to contain (C2) nonionic dye.
  • Non-ionic dyes are dyes other than acid dyes and basic dyes and do not have an ionic structure.
  • Examples of the (C2) nonionic dye include, for example. C. I. Disperse Orange 5; C.I. I. Disperse thread 58; C.I. I. Disperse Blue 165; C.I. I. Azo-based nonionic dyes such as Solvent Red 18; C. I. Bat Blue 4; C.I. I. Disperse threads 22, 60; C.I. I. Disperse Violet 26, 28, 31; C.I. I. Disperse Blue 14, 56, 60; C.I. I, Solvent Violet 13, 31, 36; C.I. I. Examples thereof include anthraquinone-based nonionic dyes such as Solvent Blue 35, 36, 45, 63, 78, 87, 97, 104 and 122.
  • the (C2) nonionic dye it is preferable to contain an anthraquinone-based nonionic dye in that the blackness (OD value) of the cured product can be increased.
  • (C3) Pigment is a coloring compound other than a dye and is insoluble in water or an organic solvent. It was
  • Examples of the (C3) pigment include organic pigments and inorganic pigments.
  • organic pigments include phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, slene pigments, indolin pigments, benzofuranone pigments, and perylene pigments.
  • aniline pigments, azo pigments, condensed azo pigments, and carbon black examples of organic pigments and inorganic pigments.
  • the inorganic pigment examples include fine particles, oxides, and composite oxides in a graphite or silver-tin alloy, or a metal such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver. , Sulfates, sulfates, nitrates, carbonates, nitrides, carbides, oxynitrides and the like.
  • the pigment to be used may be one that has been subjected to surface treatment such as rosin treatment, acid group treatment, and basic group treatment, if necessary. In some cases, it can be used together with a dispersant.
  • the dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants.
  • the content of the (C) colorant in the colored photosensitive resin composition is preferably 10 to 75 parts by mass, more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the content of the component (C) is 10 parts by mass or more, light of the corresponding wavelength can be absorbed. Further, by setting the content to 75 parts by mass or less, the residue of the opening can be reduced.
  • the content of the salt-forming compound composed of the (C1) acid dye and the basic dye in the (C) colorant is preferably 10 to 90 parts by mass, more preferably 20 to 50 parts by mass. Within this range, the residue of the opening can be further reduced and the residual film ratio can be further improved.
  • the content of the (C2) nonionic dye and / or the (C3) pigment in the (C) colorant is 10 including the content of the (C2) nonionic dye and the content of the (C3) pigment. It is preferably up to 90 parts by mass, more preferably 50 to 80 parts by mass. Within this range, the residue of the opening can be further reduced and the residual film ratio can be further improved.
  • the colored photosensitive resin composition of the present invention may contain a colorant other than the salt-forming compound composed of the above (C1) acid dye and basic dye, (C2) nonionic dye and / or (C3) pigment. good.
  • a colorant include dyes, organic pigments, and inorganic pigments, but known ones can be contained according to the purpose.
  • Coloring agents include, for example, Sumilan, Lanyl material (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Oilasperse, Zapon, Neozapon, Neptune, Acidol material (manufactured by BASF Co., Ltd.), Kayaset, and the like.
  • Kayakaran material (manufactured by Nippon Kayaku Co., Ltd.), Oil Colors, Varifast Colors, Water Colors material (manufactured by Orient Chemical Industry Co., Ltd.), Savinyl, Sandoplast, Polysinthren, Lanasin material (Clariant Chemical) Materials (manufactured by Hodoya Chemical Industry Co., Ltd.), Last Color, Oil Color materials (manufactured by Arimoto Chemical Industry Co., Ltd.), etc. can be obtained, but are not limited thereto.
  • the colored photosensitive resin composition of the present invention preferably contains (D) a thermochromic compound.
  • the thermochromic compound has a maximum absorption wavelength in the region of 350 nm or more and 700 nm or less before heating, and is not in the range of 350 nm or more and 700 nm or less. It is a compound having a wavelength in any range of 350 nm or more and 700 nm or less (hereinafter, may be referred to as “thermal color development”).
  • thermochromic compound By using the thermochromic compound, the transmittance of 350 nm or more and 700 nm or less can be significantly reduced after the heat treatment.
  • thermochromic compound (D) preferably contains a compound that is generated in the region of 350 nm or more and 700 nm or less and has a maximum absorption wavelength of 350 nm or more and 500 nm or less by heating at 120 ° C. or higher.
  • C1 Since the maximum absorption wavelength of the salt-forming compound composed of the acidic dye and the basic dye in the region of 350 nm or more and 700 nm or less is preferably 500 nm or more and 700 nm or less, even in that case, the (D) thermochromic compound is combined. This makes it possible to reduce the transmittance over a wide range in the visible light region.
  • the heat-coloring compound is preferably a heat-coloring compound that develops heat at a temperature higher than 180 ° C.
  • thermochromic compound may be a general heat-sensitive dye or a pressure-sensitive dye, or may be another compound. These thermochromic compounds develop heat by changing their chemical structure and charge state due to the action of acidic groups coexisting in the system during heat treatment at 120 ° C or higher, or 120 due to the presence of oxygen in the air. Examples thereof include those that cause a thermal oxidation reaction or the like at a temperature of ° C or higher to develop a thermal color.
  • thermochromic compound examples include triarylmethane skeleton, diarylmethane skeleton, fluorane skeleton, bislactone skeleton, phthalide skeleton, xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenoxazine skeleton, phenoxazine skeleton, and spiropyran skeleton. Be done. Specific examples thereof include the compounds described in JP-A-2004-326094. Among them, a hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferable because it has a high thermal color development temperature and excellent heat resistance.
  • the hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinone diazide compound by ester-bonding a sulfonic acid of naphthoquinone diazide to the compound.
  • the content of the (D) thermochromic compound used in the present invention is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin.
  • the content of the thermochromic compound is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet visible light region can be reduced. Further, when the content of the (D) thermochromic compound is 80 parts by mass or less, the heat resistance and strength of the cured product can be maintained and the water absorption rate can be reduced.
  • the colored photosensitive resin composition of the present invention can be used as a compound other than (A) alkali-soluble resin, (B) photoacid generator, (C) colorant, and (D) thermochromic compound, if necessary.
  • Various known additives such as a cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, and a surfactant may be contained.
  • the colored photosensitive resin composition of the present invention may contain a solvent.
  • a solvent N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2.
  • -Polar aprotonic solvents such as imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate.
  • solvents such as imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-d
  • Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, aromatic hydrocarbons such as toluene and xylene, and the like. Two or more of these may be contained.
  • the content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition in 100 parts by mass of the (A) alkali-soluble resin.
  • a colored photosensitive resin composition can be obtained by mixing a cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, a surfactant, a solvent and the like.
  • the colored photosensitive resin composition used in the method for producing a colored photosensitive resin composition film of the present invention, which will be described later, preferably contains a solvent and dissolves each of the above components. Examples of the method for promoting dissolution in such a case include heating and stirring.
  • the heating temperature is preferably set within a range that does not impair the performance of the colored photosensitive resin composition, and is usually room temperature to 80 ° C. In the present specification, the room temperature is 25 ° C. Further, the order of dissolving each component is not particularly limited, and examples thereof include a method of sequentially dissolving compounds having low solubility in a solvent.
  • the rotation speed is preferably set within a range that does not impair the performance of the colored photosensitive resin composition, and is usually 200 rpm to 2000 rpm. It may be agitated or heated as needed, and is usually at room temperature to 80 ° C.
  • components that tend to generate bubbles during stirring and dissolution such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.
  • the obtained colored photosensitive resin composition is filtered using a filtration filter to remove dust and particles.
  • the filter hole diameter is, for example, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.05 ⁇ m, 0.02 ⁇ m, and the like, but is not limited thereto.
  • the material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, but polyethylene and nylon are preferable.
  • PP polypropylene
  • PE polyethylene
  • nylon NY
  • PTFE polytetrafluoroethylene
  • the colored photosensitive resin composition contains an organic pigment, it is preferable to use a filtration filter having a pore size larger than these particle sizes.
  • the colored photosensitive resin composition of the present invention is preferably for the pixel dividing layer of the organic EL display device.
  • the cured product obtained by curing the colored photosensitive resin composition is a cured product obtained by applying the above-mentioned colored photosensitive resin composition to a substrate or the like and heat-treating the cured product.
  • the heat treatment conditions are preferably 200 ° C. or higher, more preferably 250 ° C. or higher.
  • the heat treatment conditions are preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
  • the cured product obtained by curing the colored photosensitive resin composition of the present invention preferably has a film thickness of 1.0 ⁇ m or more and 5.0 ⁇ m or less in that the blackness (OD value) of the cured product can be further increased. It is more preferably 5 ⁇ m or more and 5.0 ⁇ m or less.
  • the colored photosensitive resin composition of the present invention has sufficient alkali solubility, and even if it is a thick film, there is little residue and the pattern can be sufficiently opened.
  • the OD value per 1 ⁇ m of the cured product is preferably 0.5 or more and 2.0 or less.
  • the content of the (C) colorant is 12 to 75 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin, and the (C) colorant is composed of (C1) acid dye and basic dye.
  • the cured product can have a desired OD value.
  • the reflected chromaticity of the cured product is preferably a * value of -30 or more and 30 or less, and b * value of -30 or more and 30 or less in the CIE Lab color space display system.
  • a salt-forming compound composed of an acidic dye and a basic dye a salt-forming compound composed of an acidic dye and a basic dye having a difference in maximum absorption wavelength of 40 nm or more and 80 nm or less in a region of 350 nm or more and 700 nm or less is used. This makes it possible to obtain the desired reflected chromaticity of the cured product.
  • the a * value and the b * value are in this range, the cured product is closer to black, and the display device provided with the cured product can be made of higher quality.
  • a method for producing a cured product using the colored photosensitive resin composition of the present invention will be described.
  • the method for producing the cured product is as follows: (1) a step of applying the above-mentioned colored photosensitive resin composition to a substrate to form a coating film, and (2) an exposure of the above-mentioned coating film using an active chemical line and exposing the coating film.
  • the colored photosensitive resin composition of the present invention is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method or the like. , To obtain a coating film of a colored photosensitive resin composition.
  • the substrate to which the colored photosensitive resin composition is applied may be pretreated with the above-mentioned adhesion improving agent in advance.
  • a solution in which the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass is used.
  • a method of treating the surface of the base material can be mentioned. Examples of the method for treating the surface of the base material include methods such as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment.
  • the formed coating film is subjected to a vacuum drying treatment as necessary, and then using a hot plate, an oven, infrared rays, etc., in the range of 50 ° C to 180 ° C for 1 minute to several hours.
  • a coating film is obtained by applying the heat treatment of.
  • Irradiate the above coating film with active chemical rays (hereinafter, may be referred to as exposure). At this time, if necessary, the exposure may be performed through a photomask having a desired pattern, or the coating film may be directly exposed with a laser or the like.
  • the active chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps can be used. preferable.
  • the exposed coating film is developed with an alkaline solution to remove the exposed portion of the coating film.
  • the developing solution at this time was tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol.
  • Dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and other alkaline compounds are preferred.
  • these alkaline aqueous solutions may be mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone and dimethylacrylamide, methanol, ethanol, etc.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone and dimethylacrylamide, methanol, ethanol, etc.
  • Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added in one or more.
  • a method such as spraying, paddle, dipping, ultra
  • alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.
  • heat-treating the developed coating film By heat-treating the developed coating film, residual solvent and components with low heat resistance can be removed, so that the heat resistance and chemical resistance of the cured product can be improved.
  • This heat treatment is carried out for 5 minutes to 5 hours while selecting a certain temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. For example, a method of heat-treating at 230 ° C. for 60 minutes can be mentioned.
  • the heat treatment conditions in the present invention are preferably 200 ° C. or higher, more preferably 230 ° C. or higher.
  • the heat treatment conditions are preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
  • the display device of the present invention comprises a cured product obtained by curing the colored photosensitive resin composition.
  • the cured product obtained by curing the colored photosensitive resin composition is a display device having a substrate on which a TFT is formed, a flattening layer on a drive circuit, a pixel dividing layer and a display element on the first electrode, and a second electrode in this order. It is included in the flattening layer and the pixel dividing layer.
  • Examples of the display device having such a configuration include a liquid crystal display device and an organic EL display device. Above all, it is suitably used for an organic EL display device that requires high heat resistance and low outgassing properties for a flattening layer and a pixel dividing layer, and can be particularly preferably used for a pixel dividing layer.
  • the cured product obtained by curing the colored photosensitive resin composition of the present invention may be used for only one of the flattening layer and the pixel dividing layer, or may be used for both.
  • the active matrix type display device has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass, and has a flattening layer on the TFT so as to cover the unevenness. Further, a display element is provided on the flattening layer. The display element and the wiring are connected via a contact hole formed in the flattening layer.
  • a glass substrate manufactured by Geomatec Co., Ltd. in which the colored photosensitive resin composition (hereinafter, also referred to as varnish) prepared in Examples and Comparative Examples is formed by spattering ITO.
  • ITO substrate is coated with a spin coater (MS-A100; manufactured by Mikasa) with a spin coat so that the film thickness after prebaking is 3.0 ⁇ m, and a buzzer hot plate (HPD-3000BZN) is applied.
  • the obtained prebake film was developed with a 2.38% by mass tetramethylammonium (TMAH) aqueous solution for 60 seconds to obtain a desired film thickness, and then rinsed with pure water to obtain a developed film.
  • TMAH mass tetramethylammonium
  • the film thicknesses of the pre-baked film and the developed film were measured using a stylus type profiler (P-15; manufactured by KLA Tencor Co., Ltd.), and the residual film ratio was determined from these values by the following formula.
  • Remaining film ratio [%] (film thickness of developing film) / (film thickness of prebaked film) ⁇ 100.
  • FIGS. 1 (a) to 1 (d) The schematic diagram of the substrate used in FIGS. 1 (a) to 1 (d) is shown.
  • an ITO transparent conductive film of 10 nm was formed on the entire surface of a 38 ⁇ 46 mm non-alkali glass substrate 1 by a sputtering method, and etched as a first electrode 2.
  • an auxiliary electrode 3 was also formed at the same time in order to take out the second electrode at the same time (FIG. 1 (a)).
  • the obtained substrate was ultrasonically cleaned with "Semicoclean" (registered trademark) 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then washed with ultrapure water.
  • the photosensitive resin compositions prepared in each Example and Comparative Example were applied to the entire surface of this substrate by a spin coating method, and prebaked on a hot plate at 100 ° C. for 2 minutes.
  • the film was UV-exposed via a photomask, then developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, only the exposed portion was dissolved, and then rinsed with pure water.
  • the resulting pattern was cured in an oven at 230 ° C. under a nitrogen atmosphere for 60 minutes.
  • the pixel dividing layer 4 having an opening having a width of 70 ⁇ m and a length of 260 ⁇ m is arranged at a pitch of 155 ⁇ m in the width direction and a pitch of 465 ⁇ m in the length direction, and each opening exposes the first electrode. It was formed only in the effective area of the substrate (FIG. 1 (b)). It should be noted that this opening finally becomes a light emitting pixel.
  • the effective area of the substrate was 16 mm square, and the thickness of the insulating layer was about 1.0 ⁇ m.
  • an organic EL display device was manufactured using a substrate on which the first electrode 2, the auxiliary electrode 3, and the pixel dividing layer 4 were formed.
  • an organic EL layer 5 including a light emitting layer was formed by a vacuum vapor deposition method (FIG. 1 (c)).
  • the degree of vacuum during vapor deposition was 1 ⁇ 10 -3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition.
  • the compound (HT-1) was deposited at 10 nm as the hole injection layer, and the compound (HT-2) was deposited at 50 nm as the hole transport layer.
  • a compound as a host material (GH-1) and a compound as a dopant material (GD-1) were deposited on the light emitting layer to a thickness of 40 nm so that the doping concentration was 10%.
  • the compound (ET-1) and (LiQ) were laminated as electron transport materials at a volume ratio of 1: 1 to a thickness of 40 nm.
  • the structure of the compound used in the organic EL layer is shown below.
  • the film thickness referred to here is a crystal oscillation type film thickness monitor display value.
  • Emission area ratio [%] Area of emission area / Area of emission pixels x 100 S: Emission area ratio is 95% or more and 100% or less A: Emission area ratio is 90% or more and less than 95% B: Emission area ratio is 75% or more and less than 90% C: Emission area ratio is less than 75%.
  • the film thickness of the cure film was not 1.5 ⁇ m, it was converted into the light transmittance when the film thickness was 1.5 ⁇ m.
  • the reaction was carried out at ⁇ 15 ° C. for 4 hours, and then the temperature was returned to room temperature.
  • the precipitated white solid was collected by filtration and vacuum dried at 50 ° C.
  • 30 g of the obtained solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of 2-methoxyethanol, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and reacted at room temperature for 2 hours. After 2 hours, I confirmed that the balloon did not deflate any more.
  • the palladium compound as a catalyst was removed by filtration, distilled off under reduced pressure, and concentrated to obtain a hydroxy group-containing diamine compound (HA) having the following structure.
  • HA15.1 g (0.025 mol), BAHF 3.66 g (0.01 mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) 0.62 g (0) .0025 mol) was dissolved in 200 g of N-methylpyrrolidone (NMP).
  • NMP N-methylpyrrolidone
  • 6FDA 2,2- (3,4-dicarboxyphenyl) hexafluoropropane
  • Nonionic dye c2-1 C.I. I. Solvent blue 45 c2-2: C.I. I. Solvent blue 63 c2-3: C.I. I. Solvent Red 18 c2-4: C.I. I. Disperse Violet 31 (C3) Pigment c3-1: C.I. I. Pigment Blue 60 (C4) Other colorants c4-1: C.I. I. Acid Red 52.
  • Example 1 Under yellow light, (A) the polyimide precursor resin a-1 obtained in Synthesis Example 1 as an alkali-soluble resin, (B) the compound b-1 obtained in Synthesis Example 2 as a photoacid generator, and (C1) an acidic dye.
  • Compound c1-1 obtained in Synthesis Example 3 as a salt-forming compound composed of a basic dye, compound c2-1 as a nonionic dye, compound d-1 as a thermochromic compound, and other additives.
  • Table 1 shows the thermal cross-linking agent e-1, the compound f-1 having a phenolic hydroxyl group, the adhesion improver g-1, ⁇ -butyrolactone (GBL) and ethyl lactate (EL) as solvents in a mass ratio of 1/1. Amount was added and stirred to dissolve to prepare composition 1.
  • composition 1 the residual film ratio, opening residue, OD value and reflected chromaticity were evaluated.
  • compositions 2 to 19 were prepared with the compositions shown in Table 2 by the same method as in Example 1.
  • Compositions 2 to 19 were evaluated by the same method as in Example 1. The evaluation results are shown in Table 3.
  • Example 17 (A) 50 g of the polyimide resin a-1 obtained in Synthesis Example 1 as an alkali-soluble resin, 100 g of the compound c3-1 as a pigment (C3), and 1000 g of ⁇ -butyrolactone were charged in a tank, and the mixture was stirred with a homomixer for 20 minutes to prepare. A dispersion was obtained.
  • the obtained pre-dispersion liquid was supplied to the Ultra Apex Mill, a disperser manufactured by Hiroshima Metal & Machinery Co., Ltd., equipped with a centrifuge separator filled with 75% by volume of 0.05 mm ⁇ zirconia beads, and the rotation speed was 10 m / s for 3 hours. Dispersion was carried out to obtain a pigment dispersion liquid.
  • Thermal cross-linking agent e-1 0.6 g, compound f-1 having phenolic hydroxyl group 0.4 g, adhesion improver g-1 0.1 g, ⁇ -butyrolactone (GBL) 5.5 g as solvent, and ethyl lactate. (EL) 10 g was mixed, stirred and dissolved to prepare the composition 20.
  • composition 20 was evaluated by the same method as in Example 1. The evaluation results are shown in Table 3.
  • Example 18 In Example 2, (2) evaluation of the opening residue was made so that the thickness of the insulating layer was 3.5 ⁇ m, and (3) blackness (OD value) and (4) evaluation of the degree of reflection were heat resistance.
  • the composition 2 was evaluated by the same method except that the thickness of the colored resin film (cured product) was 3.5 ⁇ m. The evaluation results are shown in Table 3.
  • the colored photosensitive resin composition according to the present invention can form a pattern while achieving both the characteristics of residual film ratio, opening residue, and blackness.

Abstract

A purpose of the present invention is to provide a colored photosensitive resin composition which can form patterns while attaining all of the properties of film retention, aperture residue, and blackness. This colored photosensitive resin composition comprises (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the colorant (C) includes (C1) salt-forming compounds comprising an acid dye and a basic dye.

Description

着色感光性樹脂組成物、硬化物、表示装置及び硬化物の製造方法Method for manufacturing colored photosensitive resin composition, cured product, display device and cured product
　本発明は、着色感光性樹脂組成物、及びこれを用いた硬化物、表示装置、及び硬化物の製造方法に関する。さらに詳細には、半導体素子の表面保護膜、層間絶縁膜、有機エレクトロルミネッセンス（Ｅｌｅｃｔｒｏｌｕｍｉｎｅｓｃｅｎｃｅ：以下ＥＬと記す。）素子の画素分割層、有機ＥＬ素子を用いた表示装置の駆動用薄膜トランジスタ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ：以下ＴＦＴと記す。）基板の平坦化膜、回路基板の配線保護絶縁膜、固体撮像素子のオンチップマイクロレンズや各種ディスプレイ・固体撮像素子用平坦化膜、及び回路基板用ソルダーレジストなどに適した、硬化物及びこれを形成するための着色感光性樹脂組成物に関する。 The present invention relates to a colored photosensitive resin composition, a cured product using the same, a display device, and a method for producing the cured product. More specifically, a surface protective film of a semiconductor element, an interlayer insulating film, an electroluminescence (hereinafter referred to as EL) element pixel dividing layer, and a thin film transistor for driving a display device using an organic EL element. : Hereinafter referred to as TFT.) Suitable for substrate flattening film, circuit board wiring protective insulating film, on-chip microlens of solid-state image pickup element, flattening film for various displays and solid-state image pickup elements, solder resist for circuit board, etc. Further, the present invention relates to a cured product and a colored photosensitive resin composition for forming the cured product.
　ポリイミドやポリベンゾオキサゾールを含む組成物を硬化させて得られる硬化物は、半導体素子や表示装置の絶縁膜、保護膜、及び平坦化膜などに広く使用されている。その中で表示装置に使用される時、例えば有機ＥＬディスプレイの画素分割層や液晶ディスプレイのブラックマトリクスなどの用途においては、コントラストを向上させるために硬化物の光透過率を低くすることが求められている。また、表示装置の駆動用ＴＦＴへの光の進入による劣化や誤作動、リーク電流などを防ぐために、有機ＥＬディスプレイの画素分割層や有機ＥＬディスプレイのＴＦＴ基板上に設けられる平坦化膜にも透過率を低くすることが求められる。 The cured product obtained by curing a composition containing polyimide or polybenzoxazole is widely used as an insulating film, a protective film, a flattening film, etc. of semiconductor devices and display devices. Among them, when used in a display device, for example, in applications such as a pixel division layer of an organic EL display and a black matrix of a liquid crystal display, it is required to reduce the light transmission rate of the cured product in order to improve the contrast. ing. Further, in order to prevent deterioration, malfunction, leakage current, etc. due to the ingress of light into the driving TFT of the display device, it is transmitted through the pixel dividing layer of the organic EL display and the flattening film provided on the TFT substrate of the organic EL display. It is required to lower the rate.
　硬化物における４００ｎｍ以上の可視光領域の光透過率を低下させる技術としては、液晶ディスプレイ用ブラックマトリクス材料やＲＧＢペースト材料にみられるように、樹脂組成物にカーボンブラックや有機・無機顔料、染料などの着色剤を添加する方法が挙げられる。 As a technique for reducing the light transmittance in the visible light region of 400 nm or more in the cured product, as seen in black matrix materials for liquid crystal displays and RGB paste materials, carbon black, organic / inorganic pigments, dyes, etc. are added to the resin composition. A method of adding a colorant of the above can be mentioned.
　ポジ型感光性樹脂組成物において硬化物の光透過率を低下させる技術としては、例えば、ノボラック樹脂及び／又はビニル重合体からなるアルカリ可溶性樹脂にキノンジアジド化合物と黒色顔料を添加する方法（特許文献１参照）、可溶性ポリイミドに感光剤、黒色顔料を添加する方法（特許文献２参照）、アルカリ可溶性樹脂にキノンジアジド化合物、アルカリ性現像液及び有機溶剤の双方に可溶な色素を添加する方法（特許文献３参照）、感光性樹脂に黒色の油溶性染料を添加する方法（特許文献４参照）、及びアルカリ可溶性耐熱性樹脂にエステル化したキノンジアジド化合物と染料、無機顔料、有機顔料から選ばれる少なくとも１種の着色剤を添加する方法（特許文献５参照）、などがある。 As a technique for reducing the light transmittance of the cured product in the positive photosensitive resin composition, for example, a method of adding a quinonediazide compound and a black pigment to an alkali-soluble resin composed of a novolak resin and / or a vinyl polymer (Patent Document 1). (See), a method of adding a photosensitizer and a black pigment to a soluble polyimide (see Patent Document 2), and a method of adding a quinonediazide compound, an alkaline developer and a dye soluble in both an organic solvent to an alkali-soluble resin (Patent Document 3). (See), a method of adding a black oil-soluble dye to a photosensitive resin (see Patent Document 4), and at least one selected from a quinonediazide compound and a dye, an inorganic pigment, and an organic pigment esterified to an alkali-soluble heat-resistant resin. There is a method of adding a colorant (see Patent Document 5), and the like.
特開平６－２３０２１５号公報Japanese Unexamined Patent Publication No. 6-230215 特開２００３－１１９３８１号公報Japanese Patent Application Laid-Open No. 2003-119381 特開平７－２６１０１５号公報Japanese Unexamined Patent Publication No. 7-261015 特開平１０－２５４１２９号公報Japanese Unexamined Patent Publication No. 10-254129 特開２００４－１４５３２０号公報Japanese Unexamined Patent Publication No. 2004-145320
　しかしながら、これらの技術では、パターン加工した際、残膜率、開口部残渣、および黒色度のいずれかの特性が不足する課題があった。 However, these techniques have a problem that any of the characteristics of residual film ratio, opening residue, and blackness is insufficient when pattern processing is performed.
　本発明は、（Ａ）アルカリ可溶性樹脂、（Ｂ）光酸発生剤、（Ｃ）着色剤を含有する着色感光性樹脂組成物であって、該（Ｃ）着色剤が、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物を含有する、着色感光性樹脂組成物である。 The present invention is a colored photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant is a (C1) acid dye. It is a colored photosensitive resin composition containing a salt-forming compound composed of a basic dye and a basic dye.
　本発明によれば、残膜率、開口部残渣、および黒色度の特性を両立してパターン加工が可能となる。 According to the present invention, pattern processing is possible while achieving both the characteristics of residual film ratio, opening residue, and blackness.
有機ＥＬ表示装置に使用した基板の概略図である。It is a schematic diagram of the substrate used for the organic EL display device.
　本発明は、（Ａ）アルカリ可溶性樹脂、（Ｂ）光酸発生剤、（Ｃ）着色剤を含有する着色感光性樹脂組成物であって、該（Ｃ）着色剤が、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物を含有する、着色感光性樹脂組成物である。以下、本発明を詳細に説明する。 The present invention is a colored photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant is a (C1) acid dye. It is a colored photosensitive resin composition containing a salt-forming compound composed of a basic dye and a basic dye. Hereinafter, the present invention will be described in detail.
　＜（Ａ）アルカリ可溶性樹脂＞
　本発明の着色感光性樹脂組成物は、（Ａ）アルカリ可溶性樹脂を含有する。アルカリ可溶性樹脂とは、以下に定義する溶解速度が５０ｎｍ／分以上である樹脂をいう。詳細には、γ－ブチロラクトンに樹脂を溶解した溶液をシリコンウエハ上に塗布し、１２０℃で４分間プリベークを行って膜厚１０μｍ±０．５μｍのプリベーク膜を形成し、前記プリベーク膜を２３±１℃の２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液に１分間浸漬した後、純水でリンス処理したときの膜厚減少から求められる溶解速度が５０ｎｍ／分以上である樹脂をいう。 <(A) Alkali-soluble resin>
The colored photosensitive resin composition of the present invention contains (A) an alkali-soluble resin. The alkali-soluble resin means a resin having a dissolution rate of 50 nm / min or more as defined below. Specifically, a solution in which a resin is dissolved in γ-butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebake film having a film thickness of 10 μm ± 0.5 μm, and the prebake film is formed by 23 ±. A resin having a dissolution rate of 50 nm / min or more obtained from a decrease in film thickness when immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 1 ° C. for 1 minute and then rinsed with pure water.
　（Ａ）アルカリ可溶性樹脂は、アルカリ可溶性を付与するため、樹脂の構造単位中及び／又はその主鎖末端に酸性基を有することが好ましい。好ましい酸性基としてはカルボキシル基、水酸基、スルホン酸基、及びチオール基などが挙げられる。 (A) The alkali-soluble resin preferably has an acidic group in the structural unit of the resin and / or at the end of the main chain thereof in order to impart alkali solubility. Preferred acidic groups include carboxyl groups, hydroxyl groups, sulfonic acid groups, thiol groups and the like.
　（Ａ）アルカリ可溶性樹脂として具体的には、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体、フェノール樹脂、アルカリ可溶性基を有するラジカル重合性モノマーからなる重合体、シロキサンポリマー、環状オレフィン重合体、及びカルド樹脂などが挙げられる。（Ａ）アルカリ可溶性樹脂は、これらの樹脂を２種類以上含有してもよい。（Ａ）アルカリ可溶性樹脂は、耐熱性が高いものを含有することが好ましい。加えて、有機発光装置、表示装置、半導体素子に用いられる平坦化膜、画素分割層、隔壁、及び保護膜として優れた特性を得るべく、（Ａ）アルカリ可溶性樹脂は、熱処理後の２００℃以上の高温下におけるアウトガス量が少ないものを含有することが好ましい。具体的には、（Ａ）アルカリ可溶性樹脂は、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体及びそれらの共重合体からなる群より選択される一種類以上を含有することが好ましい。 (A) Specific examples of the alkali-soluble resin include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, phenol resin, a polymer composed of a radically polymerizable monomer having an alkali-soluble group, a siloxane polymer, and a cyclic olefin. Examples include polymers and cardo resins. (A) The alkali-soluble resin may contain two or more of these resins. The alkali-soluble resin (A) preferably contains a resin having high heat resistance. In addition, in order to obtain excellent properties as a flattening film, a pixel dividing layer, a partition wall, and a protective film used for an organic light emitting device, a display device, and a semiconductor element, the alkali-soluble resin (A) has a temperature of 200 ° C. or higher after heat treatment. It is preferable to contain a substance having a small amount of outgas under high temperature. Specifically, the alkali-soluble resin (A) preferably contains at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and copolymers thereof. ..
　ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体及びそれらの共重合体について説明する。ポリイミドの場合はイミド環を有するものであれば、ポリベンゾオキサゾールの場合はベンゾオキサゾール環を有するものであれば、特に限定されない。またポリイミド前駆体は、脱水閉環することによりイミド環を有するポリイミドとなる構造を有していれば、特に限定されず、ポリベンゾオキサゾール前駆体も、脱水閉環することによりベンゾオキサゾール環を有するポリベンゾオキサゾールとなる構造を有していれば、特に限定されない。 Polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymers will be described. In the case of polyimide, it is not particularly limited as long as it has an imide ring, and in the case of polybenzoxazole, it is not particularly limited as long as it has a benzoxazole ring. Further, the polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring by dehydration closing, and the polybenzoxazole precursor is also a polybenzo having a benzoxazole ring by dehydration closing. As long as it has a structure that becomes oxazole, it is not particularly limited.
　（Ａ）アルカリ可溶性樹脂としてより好ましく用いられるものとしては、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、及びポリベンゾオキサゾール前駆体が挙げられる。 (A) More preferably used as the alkali-soluble resin include polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.
　ポリイミドは一般式（１）で表される構造単位を有する。 Polyimide has a structural unit represented by the general formula (1).
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　一般式（１）中、Ｒ１は炭素原子数５～４０の４～１０価の有機基、Ｒ２は炭素原子数５～４０の２～１０価の有機基を表す。Ｒ３及びＲ４はそれぞれ独立して、水酸基、カルボキシ基、スルホン酸基、チオール基又は一般式（２）もしくは一般式（３）で表される置換基を表す。ｐは０～６の整数を表し、ｑは０～８の整数を表し、ｐ＋ｑ＞０である。 In the general formula (1), R 1 represents a 4- to 10-valent organic group having 5 to 40 carbon atoms, and R 2 represents a 2- to 10-valent organic group having 5 to 40 carbon atoms. R 3 and R 4 independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3). p represents an integer of 0 to 6, q represents an integer of 0 to 8, and p + q> 0.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　一般式（２）及び一般式（３）において、Ｒ５～Ｒ７は、それぞれ独立して、水素原子、炭素数１～１０のアルキル基、炭素数２～６のアシル基又は炭素数６～１５のアリール基を表す。上記のアルキル基、アシル基及びアリール基は、無置換体又は置換体のいずれであっても構わない。 In the general formula (2) and the general formula (3), R 5 to R 7 independently have a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 6 carbon atoms, or 6 to 6 carbon atoms. Represents 15 aryl groups. The above-mentioned alkyl group, acyl group and aryl group may be an unsubstituted or substituted product.
　ポリイミド前駆体は一般式（４）で表される構造単位を有する。 The polyimide precursor has a structural unit represented by the general formula (4).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　一般式（４）中、Ｒ８は炭素原子数５～４０の４～１０価の有機基、Ｒ９は炭素原子数５～４０の２～１０価の有機基を表す。Ｒ１０は前記一般式（２）又は一般式（３）で表される置換基を表し、Ｒ１１は水酸基、スルホン酸基、チオール基を表し、Ｒ１２は水酸基、スルホン酸基、チオール基又は一般式（２）もしくは一般式（３）で表される置換基を表す。ｒは２～８の整数を表し、ｓは０～６の整数を表し、ｔは０～８の整数を表し、２≦ｒ＋ｓ≦８である。 In the general formula (4), R 8 represents a 4- to 10-valent organic group having 5 to 40 carbon atoms, and R 9 represents a 2- to 10-valent organic group having 5 to 40 carbon atoms. R 10 represents a substituent represented by the general formula (2) or the general formula (3), R 11 represents a hydroxyl group, a sulfonic acid group, and a thiol group, and R 12 represents a hydroxyl group, a sulfonic acid group, a thiol group, or a thiol group. Represents a substituent represented by the general formula (2) or the general formula (3). r represents an integer of 2 to 8, s represents an integer of 0 to 6, t represents an integer of 0 to 8, and 2 ≦ r + s ≦ 8.
　ポリベンゾオキサゾールは一般式（５）で表される構造単位を有する。 Polybenzoxazole has a structural unit represented by the general formula (5).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　一般式（５）中、Ｒ１３は炭素原子数５～４０の２～８価の有機基、Ｒ１４は芳香族構造を有する炭素原子数５～４０の４～１０価の有機基を表す。Ｒ１５及びＲ１６はそれぞれ独立して、水酸基、カルボキシ基、スルホン酸基、チオール基又は一般式（２）もしくは一般式（３）で表される置換基を表す。ｕは０～８の整数を表し、ｖは０～６の整数を表し、ｕ＋ｖ＞０である。 In the general formula (5), R 13 represents a 2- to 8-valent organic group having 5 to 40 carbon atoms, and R 14 represents a 4- to 10-valent organic group having an aromatic structure and 5 to 40 carbon atoms. R 15 and R 16 independently represent a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group, or a substituent represented by the general formula (2) or the general formula (3). u represents an integer of 0 to 8, v represents an integer of 0 to 6, and u + v> 0.
　ポリベンゾオキサゾール前駆体は一般式（６）で表される構造単位を有する。 The polybenzoxazole precursor has a structural unit represented by the general formula (6).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　一般式（６）中、Ｒ１７は芳香族構造を有する炭素原子数５～４０の４～１０価の有機基、Ｒ１８は炭素原子数５～４０の２～１０価の有機基を表す。Ｒ１９はスルホン酸基、チオール基又は一般式（２）もしくは一般式（３）で表される置換基を表し、Ｒ２０は水酸基、カルボキシ基、スルホン酸基、チオール基又は一般式（２）もしくは一般式（３）で表される置換基を表す。ｗは２～８の整数を表し、ｘは０～８の整数を表し、ｙは０～６の整数を表し、２≦ｗ＋ｙ≦８である。 In the general formula (6), R 17 represents a 4- to 10-valent organic group having an aromatic structure and having 5 to 40 carbon atoms, and R 18 represents a 2- to 10-valent organic group having 5 to 40 carbon atoms. R 19 represents a sulfonic acid group, a thiol group or a substituent represented by the general formula (2) or the general formula (3), and R 20 is a hydroxyl group, a carboxy group, a sulfonic acid group, a thiol group or a general formula (2). Alternatively, it represents a substituent represented by the general formula (3). w represents an integer of 2 to 8, x represents an integer of 0 to 8, y represents an integer of 0 to 6, and 2 ≦ w + y ≦ 8.
　ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体及びそれらの共重合体からなる群より選択される１種以上は、上記一般式（１）、一般式（４）、一般式（５）又は一般式（６）で表される構造単位を５～１００，０００有することが好ましい。また、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体及びそれらの共重合体からなる群より選択される１種以上は、上記一般式（１）、一般式（４）、一般式（５）又は一般式（６）で表される構造単位に加えて、他の構造単位を有してもよい。この場合、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体及びそれらの共重合体からなる群より選択される１種以上は、上記一般式（１）、一般式（４）、一般式（５）又は一般式（６）で表される構造単位を、全構造単位数のうち５０モル％以上有することが好ましく、７０モル％以上有することがより好ましい。 One or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymers are the above general formulas (1), general formulas (4) and general formulas (5). ) Or the structural unit represented by the general formula (6) is preferably 5 to 100,000. Further, one or more selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and their copolymers are the above general formulas (1), general formulas (4) and general formulas. In addition to the structural unit represented by (5) or the general formula (6), other structural units may be included. In this case, at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and a copolymer thereof is the above general formula (1), general formula (4), general. It is preferable to have 50 mol% or more of the total number of structural units, and more preferably 70 mol% or more, of the structural units represented by the formula (5) or the general formula (6).
　一般式（１）中のＲ１－（Ｒ３）ｐ、及び一般式（４）中の（Ｒ１０）ｒ－Ｒ８－（Ｒ１１）ｓはテトラカルボン酸又はその誘導体の残基を表す。テトラカルボン酸誘導体の残基としては、テトラカルボン酸二無水物、テトラカルボン酸二塩化物又はテトラカルボン酸活性ジエステルの残基が挙げられる。 R 1- (R 3 ) p in the general formula (1) and (R 10 ) r -R 8- (R 11 ) s in the general formula (4) represent residues of the tetracarboxylic acid or its derivative. .. Residues of the tetracarboxylic acid derivative include residues of tetracarboxylic acid dianhydride, tetracarboxylic acid dichloride or tetracarboxylic acid active diester.
　テトラカルボン酸及びその誘導体の残基としては、ピロメリット酸、３，３’，４，４’－ビフェニルテトラカルボン酸、２，３，３’，４’－ビフェニルテトラカルボン酸、２，２’，３，３’－ビフェニルテトラカルボン酸、３，３’，４，４’－ベンゾフェノンテトラカルボン酸、２，２’，３，３’－ベンゾフェノンテトラカルボン酸、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン、２，２－ビス（２，３－ジカルボキシフェニル）ヘキサフルオロプロパン、１，１－ビス（３，４－ジカルボキシフェニル）エタン、１，１－ビス（２，３－ジカルボキシフェニル）エタン、ビス（３，４－ジカルボキシフェニル）メタン、ビス（２，３－ジカルボキシフェニル）メタン、ビス（３，４－ジカルボキシフェニル）エーテル、１，２，５，６－ナフタレンテトラカルボン酸、２，３，６，７－ナフタレンテトラカルボン酸、２，３，５，６－ピリジンテトラカルボン酸、３，４，９，１０－ペリレンテトラカルボン酸及び下記に示した構造の芳香族テトラカルボン酸の残基や、ブタンテトラカルボン酸、１，２，３，４－シクロペンタンテトラカルボン酸などの脂肪族のテトラカルボン酸の残基、又は、それらのテトラカルボン酸二無水物、テトラカルボン酸二塩化物若しくはテトラカルボン酸活性ジエステルの残基などが挙げられる。 Residues of tetracarboxylic acid and its derivatives include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2'. , 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4) -Dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2) , 3-Dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) ether, 1,2,5 , 6-Naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid and shown below Residues of aromatic tetracarboxylic acids having a similar structure, residues of aliphatic tetracarboxylic acids such as butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, or tetracarboxylic acids thereof. Examples thereof include residues of dianhydride, tetracarboxylic acid dichloride or tetracarboxylic acid active diester.
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式中、Ｒ２１は酸素原子、Ｃ（ＣＦ３）２、又はＣ（ＣＨ３）２を表す。Ｒ２２及びＲ２３はそれぞれ独立に水素原子、又は水酸基を表す。 In the formula, R 21 represents an oxygen atom, C (CF 3 ) 2 , or C (CH 3 ) 2 . R 22 and R 23 independently represent a hydrogen atom or a hydroxyl group, respectively.
　上記一般式（５）中のＲ１３－（Ｒ１５）ｕ、及び一般式（６）中のＲ１７－（Ｒ１９）ｘはジカルボン酸又はその誘導体の残基を表す。ジカルボン酸誘導体の残基としては、ジカルボン酸無水物、ジカルボン酸塩化物、ジカルボン酸活性エステル、トリカルボン酸無水物、トリカルボン酸塩化物、トリカルボン酸活性エステル、ジホルミル化合物の残基が挙げられる。 R 13- (R 15 ) u in the general formula (5) and R 17- (R 19 ) x in the general formula (6) represent residues of a dicarboxylic acid or a derivative thereof. Examples of the residue of the dicarboxylic acid derivative include residues of a dicarboxylic acid anhydride, a dicarboxylic acid acid compound, a dicarboxylic acid active ester, a tricarboxylic acid anhydride, a tricarboxylic acid acid compound, a tricarboxylic acid active ester, and a diformyl compound.
　ジカルボン酸及びその誘導体の残基としては、テレフタル酸、イソフタル酸、ジフェニルエーテルジカルボン酸、ビス（カルボキシフェニル）ヘキサフルオロプロパン、ビフェニルジカルボン酸、ベンゾフェノンジカルボン酸、トリフェニルジカルボン酸など、又は、それらのジカルボン酸無水物、ジカルボン酸塩化物、ジカルボン酸活性エステルの残基などが挙げられる。また、トリカルボン酸及びその誘導体の残基としては、トリメリット酸、トリメシン酸、ジフェニルエーテルトリカルボン酸、ビフェニルトリカルボン酸など、又は、それらのトリカルボン酸無水物、トリカルボン酸塩化物、トリカルボン酸活性エステルの残基などが挙げられる。 Examples of the residue of the dicarboxylic acid and its derivative include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenone dicarboxylic acid, triphenyldicarboxylic acid, and the like, or dicarboxylic acids thereof. Examples thereof include anhydrides, dicarboxylic acid salts, residues of dicarboxylic acid active esters, and the like. The residues of the tricarboxylic acid and its derivatives include trimellitic acid, trimethic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid, etc., or the residues of their tricarboxylic acid anhydrides, tricarboxylic acid salts, and tricarboxylic acid active esters. And so on.
　一般式（１）中のＲ２－（Ｒ４）ｑ及び一般式（４）中のＲ９－（Ｒ１２）ｔは、ジアミン又はその誘導体の残基を表す。 R 2- (R 4 ) q in the general formula (1) and R 9- (R 12 ) t in the general formula (4) represent residues of diamines or derivatives thereof.
　また、一般式（５）中のＲ１４－（Ｒ１６）ｖ及び一般式（６）中の（ＯＨ）ｗ－Ｒ１８－（Ｒ２０）ｙは、ビスアミノフェノール化合物又はその誘導体残基を表す。ビスアミノフェノール化合物誘導体の残基としては、ジイソシアネート化合物又はトリメチルシリル化ジアミンが挙げられる。 Further, R 14- (R 16 ) v in the general formula (5) and (OH) w -R 18- (R 20 ) y in the general formula (6) are bisaminophenol compounds or derivative residues thereof. show. Examples of the residue of the bis-aminophenol compound derivative include a diisocyanate compound and a trimethylsilylated diamine.
　ビスアミノフェノール化合物及びその誘導体の残基としては、３，４’－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル、３，４’－ジアミノジフェニルメタン、４，４’－ジアミノジフェニルメタン、１，４－ビス（４－アミノフェノキシ）ベンゼン、ベンジジン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、１，５－ナフタレンジアミン、２，６－ナフタレンジアミン、ビス（４－アミノフェノキシ）ビフェニル、ビス｛４－（４－アミノフェノキシ）フェニル｝エーテル、１，４－ビス（４－アミノフェノキシ）ベンゼン、２，２’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジエチル－４，４’－ジアミノビフェニル、３，３’－ジメチル－４，４’－ジアミノビフェニル、３，３’－ジエチル－４，４’－ジアミノビフェニル、２，２’，３，３’－テトラメチル－４，４’－ジアミノビフェニル、３，３’，４，４’－テトラメチル－４，４’－ジアミノビフェニル、２，２’－ジ（トリフルオロメチル）－４，４’－ジアミノビフェニル、９，９－ビス（４－アミノフェニル）フルオレン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２’－ビス（トリフルオロメチル）－３，３’－ジヒドロキシベンジジン、２，２’－ビス（トリフルオロメチル）－５，５’－ジヒドロキシベンジジンあるいはこれらの芳香族環の水素原子の少なくとも一部をアルキル基、水酸基又はハロゲン原子で置換した化合物や、脂肪族のシクロヘキシルジアミン、メチレンビスシクロヘキシルアミン及び下記に示した構造のジアミンの残基などが挙げられる。（Ａ）アルカリ可溶性樹脂はこれらを２種以上有してもよい。 The residues of the bisaminophenol compound and its derivatives include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 1,4-bis. (4-Aminophenoxy) Benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis {4- (4- (4-) Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl , 3,3', 4,4'-Tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 9,9-bis (4-) Aminophenyl) fluorene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) -3,3'-dihydroxybenzidine, 2,2'-bis (Trifluoromethyl) -5,5'-dihydroxybenzidine or compounds in which at least a part of the hydrogen atom of these aromatic rings is replaced with an alkyl group, a hydroxyl group or a halogen atom, or an aliphatic cyclohexyldiamine or methylenebiscyclohexylamine. And residues of diamine having the structure shown below. (A) The alkali-soluble resin may have two or more of these.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式中、Ｒ２１は酸素原子、Ｃ（ＣＦ３）２、又はＣ（ＣＨ３）２を表す。Ｒ２２～Ｒ２５はそれぞれ独立に水素原子、又は水酸基を表す。 In the formula, R 21 represents an oxygen atom, C (CF 3 ) 2 , or C (CH 3 ) 2 . R 22 to R 25 independently represent a hydrogen atom or a hydroxyl group, respectively.
　また、これらのアルカリ可溶性樹脂の末端を、酸性基を有するモノアミン、酸無水物、酸クロリド、モノカルボン酸により封止することで、主鎖末端に酸性基を有するアルカリ可溶性樹脂を得ることができる。 Further, by sealing the ends of these alkali-soluble resins with a monoamine having an acidic group, an acid anhydride, an acid chloride, or a monocarboxylic acid, an alkali-soluble resin having an acidic group at the end of the main chain can be obtained. ..
　このような酸性基を有するモノアミンの好ましい例としては、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノールなどが挙げられる。これらを２種以上用いてもよい。 Preferred examples of monoamines having such acidic groups are 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino. Examples thereof include -4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like. Two or more of these may be used.
　また、このような酸無水物、酸クロリド、モノカルボン酸の好ましい例としては、無水フタル酸、無水マレイン酸、ナジック酸無水物、シクロヘキサンジカルボン酸無水物、３－ヒドロキシフタル酸無水物などの酸無水物、３－カルボキシフェノール、４－カルボキシフェノール、３－カルボキシチオフェノール、４－カルボキシチオフェノールなどのモノカルボン酸類及びこれらのカルボキシル基が酸クロリド化したモノ酸クロリド化合物、モノ酸クロリド化合物とＮ－ヒドロキシベンゾトリアゾールやＮ－ヒドロキシ－５－ノルボルネン－２，３－ジカルボキシイミドとの反応により得られる活性エステル化合物が挙げられる。これらを２種以上用いてもよい。 In addition, preferred examples of such acid anhydrides, acid chlorides, and monocarboxylic acids include acids such as phthalic anhydride, maleic anhydride, nagic acid anhydride, cyclohexanedicarboxylic acid anhydride, and 3-hydroxyphthalic acid anhydride. Anhydrides, monocarboxylic acids such as 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, monoacid chloride compounds in which these carboxyl groups are acid chlorides, monoacid chloride compounds and N. Examples thereof include active ester compounds obtained by reaction with -hydroxybenzotriazole and N-hydroxy-5-norbornene-2,3-dicarboxyimide. Two or more of these may be used.
　着色感光性樹脂組成物に用いられる（Ａ）アルカリ可溶性樹脂は公知の方法により合成される。ポリイミド前駆体、例えばポリアミド酸やポリアミド酸エステルなどの場合、製造方法として例えば、低温中でテトラカルボン酸二無水物とジアミン化合物を反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後アミンと縮合剤の存在下で反応させる方法、テトラカルボン酸二無水物とアルコールとによりジエステルを得、その後残りのジカルボン酸を酸クロリド化し、アミンと反応させる方法などで合成することができる。 The (A) alkali-soluble resin used in the colored photosensitive resin composition is synthesized by a known method. In the case of a polyimide precursor, for example, polyamic acid or polyamic acid ester, as a production method, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, or a method of reacting a tetracarboxylic acid dianhydride with an alcohol to obtain a diester is obtained. Then, it can be synthesized by a method of reacting with an amine in the presence of a condensing agent, a method of obtaining a diester by tetracarboxylic acid dianhydride and an alcohol, and then acid chlorideizing the remaining dicarboxylic acid and reacting with the amine. ..
　ポリイミドの場合、例えば前述の方法で得られたポリアミド酸又はポリアミド酸エステルを加熱あるいは酸や塩基などの化学処理で脱水閉環することにより得ることができる。 In the case of polyimide, it can be obtained, for example, by dehydrating and closing the polyamic acid or polyamic acid ester obtained by the above method by heating or chemical treatment with an acid or a base.
　ポリベンゾオキサゾール前駆体、例えばポリヒドロキシアミドなどの場合、製造方法としては、ビスアミノフェノール化合物とジカルボン酸を縮合反応させることで得ることが出来る。具体的には、ジシクロヘキシルカルボジイミド（ＤＣＣ）のような脱水縮合剤と酸を反応させ、ここにビスアミノフェノール化合物を加える方法やピリジンなどの３級アミンを加えたビスアミノフェノール化合物の溶液にジカルボン酸ジクロリドの溶液を滴下するなどがある。 In the case of a polybenzoxazole precursor, for example, polyhydroxyamide, it can be obtained by subjecting a bisaminophenol compound to a dicarboxylic acid in a condensation reaction. Specifically, a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a bisaminophenol compound thereto, or a dicarboxylic acid in a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. For example, a solution of dichloride is dropped.
　ポリベンゾオキサゾールの場合、例えば前述の方法で得られたポリヒドロキシアミドなどを加熱あるいは酸や塩基などの化学処理で脱水閉環することにより得ることができる。 In the case of polybenzoxazole, for example, it can be obtained by dehydrating and ring-closing the polyhydroxyamide obtained by the above-mentioned method by heating or chemical treatment with an acid or a base.
　＜（Ｂ）光酸発生剤＞
　本発明の着色感光性樹脂組成物は、（Ｂ）光酸発生剤を含有する。（Ｂ）光酸発生剤としては、キノンジアジド化合物、スルホニウム塩、ホスホニウム塩、ジアゾニウム塩、ヨードニウム塩などが挙げられ、キノンジアジド化合物であることが好ましい。 <(B) Photoacid generator>
The colored photosensitive resin composition of the present invention contains (B) a photoacid generator. Examples of the (B) photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like, and quinonediazide compounds are preferable.
　キノンジアジド化合物としては、ポリヒドロキシ化合物やポリアミノ化合物にキノンジアジドのスルホン酸がエステル結合したもの、ポリヒドロキシ化合物にキノンジアジドのスルホン酸がスルホンアミド結合したもの、ポリヒドロキシポリアミノ化合物にキノンジアジドのスルホン酸がエステル結合及び／又はスルホンアミド結合したものなどが挙げられる。キノンジアジド化合物にかかる、ポリヒドロキシ化合物やポリアミノ化合物のヒドロキシ基およびアミノ基全体１００モル％に対して、５０モル％以上がキノンジアジドのスルホン酸と結合していることが好ましい。５０モル％以上置換されているキノンジアジド化合物を使用することで、キノンジアジド化合物のアルカリ水溶液に対する親和性が低下し、未露光部の樹脂組成物のアルカリ水溶液に対する溶解性を大きく低下させるとともに、露光によりキノンジアジドスルホニル基がインデンカルボン酸に変化し、露光部の樹脂組成物のアルカリ水溶液に対する大きな溶解速度を得ることができ、結果として組成物の露光部と未露光部の溶解速度比を大きくして、高い解像度でパターンを得ることができる。このようなキノンジアジド化合物を用いることで、一般的な水銀灯のｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）に感光するポジ型の感光性樹脂組成物を得ることができる。また、光酸発生剤は単独で使用しても、２種以上組み合わせて使用してもよく、高感度な感光性樹脂組成物を得ることができる。 The quinone-diazide compound includes a polyhydroxy compound or a polyamino compound with an ester bond of quinone-diazide sulfonic acid, a polyhydroxy compound with a sulfonic acid of quinone-diazide bonded with a sulfonamide, and a polyhydroxypolyamino compound with an ester bond of quinone-diazide sulfonic acid. / Or a sulfonamide-bonded substance or the like. It is preferable that 50 mol% or more of the hydroxy group of the polyhydroxy compound or the polyamino compound and 100 mol% of the total amino groups of the quinone diazide compound are bonded to the sulfonic acid of the quinone diazide. By using the quinone diazide compound substituted in an amount of 50 mol% or more, the affinity of the quinone diazide compound with respect to the alkaline aqueous solution is lowered, the solubility of the unexposed resin composition in the alkaline aqueous solution is greatly lowered, and the quinone diazide is exposed by exposure. The sulfonyl group is changed to indencarboxylic acid, and a large dissolution rate of the resin composition of the exposed portion in the alkaline aqueous solution can be obtained. As a result, the dissolution rate ratio of the exposed portion and the unexposed portion of the composition is increased to be high. You can get the pattern at the resolution. By using such a quinone diazide compound, a positive photosensitive resin composition that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general mercury lamp can be obtained. Further, the photoacid generator may be used alone or in combination of two or more, and a highly sensitive photosensitive resin composition can be obtained.
　キノンジアジドは５－ナフトキノンジアジドスルホニル基、４－ナフトキノンジアジドスルホニル基のいずれも好ましく用いられる。５－ナフトキノンジアジドスルホニルエステル化合物は水銀灯のｇ線領域まで吸収が伸びており、ｇ線露光及び全波長露光に適している。４－ナフトキノンジアジドスルホニルエステル化合物は水銀灯のｉ線領域に吸収を持っており、ｉ線露光に適している。本発明においては、露光する波長によって４－ナフトキノンジアジドスルホニルエステル化合物、又は５－ナフトキノンジアジドスルホニルエステル化合物を選択することが好ましい。また、同一分子中に４－ナフトキノンジアジドスルホニル基、５－ナフトキノンジアジドスルホニル基を併用した、ナフトキノンジアジドスルホニルエステル化合物を得ることもできるし、４－ナフトキノンジアジドスルホニルエステル化合物と５－ナフトキノンジアジドスルホニルエステル化合物を併用することもできる。 As the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure and all-wavelength exposure. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, it is also possible to obtain a naphthoquinone diazidosulfonyl ester compound in which a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group are used in combination in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound. Can also be used together.
　（Ｂ）光酸発生剤の分子量は、熱処理により得られる硬化物の耐熱性、機械特性、接着性の点から、好ましくは３００以上、より好ましくは３５０以上であり、好ましくは３０００以下、より好ましくは１５００以下である。 (B) The molecular weight of the photoacid generator is preferably 300 or more, more preferably 350 or more, preferably 3000 or less, more preferably 3000 or less, from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the cured product obtained by heat treatment. Is 1500 or less.
　（Ｂ）光酸発生剤の含有量は、（Ａ）アルカリ可溶性樹脂１００質量部に対して、好ましくは１質量部以上、より好ましくは３質量部以上であり、好ましくは１００質量部以下、より好ましくは８０質量部以下である。１～１００質量部であれば、熱処理後の硬化物の耐熱性、耐薬品性、機械特性を維持しつつ、感光性を付与することができる。 The content of the (B) photoacid generator is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 100 parts by mass or less, based on 100 parts by mass of the (A) alkali-soluble resin. It is preferably 80 parts by mass or less. If it is 1 to 100 parts by mass, it is possible to impart photosensitivity while maintaining the heat resistance, chemical resistance and mechanical properties of the cured product after heat treatment.
　＜（Ｃ）着色剤＞
　本発明の着色感光性樹脂組成物は、（Ｃ）着色剤を含有し、該（Ｃ）着色剤は、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物を含有する。 <(C) Colorant>
The colored photosensitive resin composition of the present invention contains (C) a colorant, and the (C) colorant contains a salt-forming compound composed of (C1) an acid dye and a basic dye.
　＜（Ｃ１）酸性染料と塩基性染料からなる造塩化合物＞
　（Ｃ１）酸性染料と塩基性染料からなる造塩化合物とは、酸性染料と塩基性染料を反応させて得られる化合物である。染料イオンがアニオン性である酸性染料と、染料イオンがカチオン性である塩基性染料との化学（造塩）反応により得られる化合物であり、化学的に安定である。本発明の着色感光性樹脂組成物は、酸性染料と塩基性染料をそれぞれ単独に含有するのでなく、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物を含有する。造塩化合物として含有することで、酸性染料と塩基性染料をそれぞれ単独に含有する場合と比較して、酸性染料と塩基性染料それぞれの対イオンを含有しないので、好ましい。 <(C1) Salt-forming compound consisting of acid dye and basic dye>
(C1) The salt-forming compound composed of an acid dye and a basic dye is a compound obtained by reacting an acid dye with a basic dye. It is a compound obtained by a chemical (salt-forming) reaction between an acidic dye having an anionic dye ion and a basic dye having a cationic dye ion, and is chemically stable. The colored photosensitive resin composition of the present invention does not contain an acid dye and a basic dye individually, but contains (C1) a salt-forming compound composed of an acid dye and a basic dye. The inclusion as a salt-forming compound is preferable because it does not contain the counter ions of the acid dye and the basic dye as compared with the case where the acid dye and the basic dye are contained alone.
　＜酸性染料＞
　酸性染料とは、分子中にスルホ基やカルボキシ基などの酸性の置換基を有する化合物か、又はその塩であるアニオン性の水溶性染料である。なお酸性染料としては、狭義の酸性染料だけでなく、スルホ基やカルボキシ基などの酸性の置換基を有していれば、直接染料に分類されるもの等を含む。 <Acid dye>
The acid dye is a compound having an acidic substituent such as a sulfo group or a carboxy group in the molecule, or an anionic water-soluble dye which is a salt thereof. The acid dye includes not only acid dyes in a narrow sense but also those directly classified as dyes if they have an acidic substituent such as a sulfo group or a carboxy group.
　酸性染料としては、例えば、Ｃ．Ｉ．アシッドイエロー１、１７、１８、２３、２５、３６、３８、４２、４４、５４、５９、７２、７８、１５１；Ｃ．Ｉ．アシッドオレンジ７、１０、１２、１９、２０、２２、２８、３０、５２、５６、７４、１２７；Ｃ．Ｉ．アシッドレッド１、３、４、６、８、１１、１２、１４、１８、２６、２７、３３、３７、５３、５７、８８、１０６、１０８、１１１、１１４、１３１、１３７、１３８、１５１、１５４、１５８、１５９、１７３、１８４、１８６、２１５、２５７、２６６、２９６、３３７；Ｃ．Ｉ．アシッドブラウン２、４、１３、２４８；Ｃ．Ｉ．アシッドバイオレット１１、５６、５８；Ｃ．Ｉ．アシッドブルー９２、１０２、１１３、１１７などのアゾ系酸性染料；
Ｃ．Ｉ．アシッドイエロー２、３、５などのキノリン系酸性染料；
Ｃ．Ｉ．アシッドレッド５０、５１、５２、８７、９１、９２、９３、９４、２８９などのキサンテン系酸性染料；
Ｃ．Ｉ．アシッドレッド８２、９２；Ｃ．Ｉ．アシッドバイオレット４１、４２、４３；Ｃ．Ｉ．アシッドブルー１４、２３、２５、２７、４０、４５、７８、８０、１２７：１、１２９、１４５、１６７、２３０；Ｃ．Ｉ．アシッドグリーン２５、２７などのアントラキノン系酸性染料；
Ｃ．Ｉ．アシッドバイオレット１７、４９；Ｃ．Ｉ．アシッドブルー７、９、１５、２２、８３、９０；Ｃ．Ｉ．アシッドグリーン９、５０；Ｃ．Ｉ．フードグリーン３等のトリアリールメタン系酸性染料；
Ｃ．Ｉ．アシッドブルー２４９などのフタロシアニン系酸性染料；
Ｃ．Ｉ．アシッドブルー７４などのインジゴイド系酸性染料；
Ｃ．Ｉ．ダイレクトイエロー４、８、９、２６、４４；Ｃ．Ｉ．ダイレクトレッド２、６、２３、２８、７９、８０、８１；Ｃ．Ｉ．ダイレクトバイオレット１、３９；Ｃ．Ｉ．ダイレクトブルー２、１４、１５、７１、１６８；Ｃ．Ｉ．ダイレクトグリーン５９などの直接染料などが挙げられる。 Examples of the acid dye include C.I. I. Acid Yellow 1, 17, 18, 23, 25, 36, 38, 42, 44, 54, 59, 72, 78, 151; C.I. I. Acid Orange 7, 10, 12, 19, 20, 22, 28, 30, 52, 56, 74, 127; C.I. I. Acid Red 1, 3, 4, 6, 8, 11, 12, 14, 18, 26, 27, 33, 37, 53, 57, 88, 106, 108, 111, 114, 131, 137, 138, 151, 154, 158, 159, 173, 184, 186, 215, 257, 266, 296, 337; C.I. I. Acid Brown 2, 4, 13, 248; C.I. I. Acid Violet 11, 56, 58; C.I. I. Azo-based acid dyes such as acid blue 92, 102, 113, 117;
C. I. Quinoline acid dyes such as Acid Yellow 2, 3, 5;
C. I. Xanthene acid dyes such as Acid Red 50, 51, 52, 87, 91, 92, 93, 94, 289;
C. I. Acid Red 82, 92; C.I. I. Acid Violet 41, 42, 43; C.I. I. Acid Blue 14, 23, 25, 27, 40, 45, 78, 80, 127: 1, 129, 145, 167, 230; C.I. I. Anthraquinone-based acid dyes such as Acid Green 25 and 27;
C. I. Acid Violet 17, 49; C.I. I. Acid Blue 7, 9, 15, 22, 83, 90; C.I. I. Acid Green 9, 50; C.I. I. Triarylmethane acid dyes such as Food Green 3;
C. I. Phthalocyanine acid dyes such as Acid Blue 249;
C. I. Indigoid acid dyes such as Acid Blue 74;
C. I. Direct Yellow 4, 8, 9, 26, 44; C.I. I. Direct Red 2, 6, 23, 28, 79, 80, 81; C.I. I. Direct Violet 1, 39; C.I. I. Direct Blue 2, 14, 15, 71, 168; C.I. I. Examples include direct dyes such as Direct Green 59.
　中でも、酸性染料は、開口部残渣を少なくできる点で、キサンテン系酸性染料及び／又はトリアリールメタン系酸性染料を含有することが好ましい。開口部残渣をより少なくできる点で、Ｃ．Ｉ．アシッドレッド５０、５２、２８９などのキサンテン系酸性染料を含有することがより好ましい。また、キサンテン系酸性染料は、硬化物の黒色度（ＯＤ値）を高くできる点で、Ｃ．Ｉ．アシッドレッド５２を含有することがさらに好ましい。 Among them, the acid dye preferably contains a xanthene-based acid dye and / or a triarylmethane-based acid dye in that the opening residue can be reduced. C.I. I. It is more preferable to contain a xanthene-based acid dye such as Acid Red 50, 52, 289. Further, the xanthene-based acid dye can increase the blackness (OD value) of the cured product, and thus C.I. I. It is more preferable to contain Acid Red 52.
　酸性染料は、ナトリウム塩としたときの２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液への溶解度が、４質量％以上９質量％以下であることが好ましい。これを満たす酸性染料を用いた造塩化合物は、残膜率を高くしつつ開口部残渣をより少なくできる。 The acid dye preferably has a solubility in a 2.38% by mass tetramethylammonium hydroxide aqueous solution as a sodium salt of 4% by mass or more and 9% by mass or less. A salt-forming compound using an acid dye satisfying this can increase the residual film ratio and reduce the amount of opening residue.
　酸性染料がナトリウム塩以外の塩であった場合、ナトリウム型陽イオン交換樹脂などを用いることで、酸性染料をナトリウム塩とすることができる。２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液への溶解度は、２５℃下において該水溶液へ酸性染料のナトリウム塩を少量ずつ投入し攪拌溶解させ、溶け残りが生じない限界の投入量から求めることができる。 When the acid dye is a salt other than the sodium salt, the acid dye can be made into a sodium salt by using a sodium type cation exchange resin or the like. The solubility in a 2.38 mass% tetramethylammonium hydroxide aqueous solution can be determined from the limit amount of the acid dye sodium salt added little by little to the aqueous solution at 25 ° C. and dissolved by stirring. can.
　また、酸性染料のアニオン部の酸性基の数は、酸性染料におけるアニオン部の分子量１０００あたり、２以上６以下であることが好ましい。これを満たす酸性染料を用いた造塩化合物は、残膜率を高くしつつ開口部残渣をより少なくできる。アニオン部の分子量は構造式から計算で求めることができる。 Further, the number of acidic groups in the anion portion of the acid dye is preferably 2 or more and 6 or less per 1000 molecular weight of the anion portion in the acid dye. A salt-forming compound using an acid dye satisfying this can increase the residual film ratio and reduce the amount of opening residue. The molecular weight of the anion portion can be calculated from the structural formula.
　＜塩基性染料＞
　塩基性染料とは、分子中にアミノ基やイミノ基などの塩基性の置換基を有する化合物か、又はその塩であるカチオン性の水溶性染料である。 <Basic dye>
The basic dye is a compound having a basic substituent such as an amino group or an imino group in the molecule, or a cationic water-soluble dye which is a salt thereof.
　塩基性染料としては、例えば、
Ｃ．Ｉ．ベーシックレッド１７、２２、２３、２５、２９、３０、３８、３９、４６、４６：１、８２；Ｃ．Ｉ．ベーシックオレンジ２、２４、２５；Ｃ．Ｉ．ベーシックバイオレット１８；Ｃ．Ｉ．ベーシックイエロー１５、２４、２５、３２、３６、４１、７３、８０；Ｃ．Ｉ．ベーシックブラウン１；Ｃ．Ｉ．ベーシックブルー４１、５４、６４、６６、６７、１２９などのアゾ系塩基性染料；
Ｃ．Ｉ．ベーシックレッド１、２；Ｃ．Ｉ．ベーシックバイオレット１０、１１などのキサンテン系塩基性染料；
Ｃ．Ｉ．ベーシックイエロー１１、１３、２１、２３、２８；Ｃ．Ｉ．ベーシックオレンジ２１；Ｃ．Ｉ．ベーシックレッド１３、１４；Ｃ．Ｉ．ベーシックバイオレット１６、３９；などのメチン系塩基性染料；
Ｃ．Ｉ．ベーシックブルー２２、３５、４５、４７などのアントラキノン系塩基性染料；
Ｃ．Ｉ．ベーシックバイオレット１、２、３、４、１３、１４、２３；Ｃ．Ｉ．ベーシックブルー１、５、７、８、１１、１５、１８、２１、２４、２６；Ｃ．Ｉ．ベーシックグリーン１、４などのトリアリールメタン系塩基性染料が挙げられる。 As a basic dye, for example,
C. I. Basic Red 17, 22, 23, 25, 29, 30, 38, 39, 46, 46: 1, 82; C.I. I. Basic Orange 2, 24, 25; C.I. I. Basic Violet 18; C.I. I. Basic Yellow 15, 24, 25, 32, 36, 41, 73, 80; C.I. I. Basic Brown 1; C.I. I. Azo-based basic dyes such as Basic Blue 41, 54, 64, 66, 67, 129;
C. I. Basic Red 1, 2; C.I. I. Xanthene-based basic dyes such as Basic Violet 10, 11;
C. I. Basic Yellow 11, 13, 21, 23, 28; C.I. I. Basic Orange 21; C.I. I. Basic Red 13, 14; C.I. I. Methine-based basic dyes such as Basic Violet 16, 39;
C. I. Anthraquinone-based basic dyes such as Basic Blue 22, 35, 45, 47;
C. I. Basic Violet 1, 2, 3, 4, 13, 14, 23; C.I. I. Basic Blue 1, 5, 7, 8, 11, 15, 18, 21, 24, 26; C.I. I. Examples thereof include triarylmethane-based basic dyes such as Basic Greens 1 and 4.
　中でも、塩基性染料は、硬化物の黒色度（ＯＤ値）を高くできる点で、キサンテン系塩基性染料及び／又はトリアリールメタン系塩基性染料を含有することが好ましく、トリアリールメタン系塩基性染料であることがより好ましい。トリアリールメタン系塩基性染料は、硬化物の黒色度（ＯＤ値）をより高くできる点で、Ｃ．Ｉ．ベーシックブルー７及び／又はＣ．Ｉ．ベーシックブルー２６を含有することがさらに好ましい。 Among them, the basic dye preferably contains a xanthene-based basic dye and / or a triarylmethane-based basic dye in that the blackness (OD value) of the cured product can be increased, and is preferably a triarylmethane-based basic dye. It is more preferably a dye. Triarylmethane-based basic dyes can increase the blackness (OD value) of the cured product, and thus C.I. I. Basic Blue 7 and / or C.I. I. It is more preferable to contain Basic Blue 26.
　前述の通り、酸性染料は、キサンテン系酸性染料及び／又はトリアリールメタン系酸性染料を含有することが好ましい。そして、塩基性染料は、キサンテン系塩基性染料及び／又はトリアリールメタン系塩基性染料を含有することが好ましい。酸性染料及び塩基性染料は、いずれもキサンテン系塩基性染料及び／又はトリアリールメタン系塩基性染料を含有することが好ましい。つまり、酸性染料及び／又は塩基性染料が、キサンテン系染料及び／又はトリアリールメタン系染料を含有することが好ましい。 As described above, the acid dye preferably contains a xanthene-based acid dye and / or a triarylmethane-based acid dye. The basic dye preferably contains a xanthene-based basic dye and / or a triarylmethane-based basic dye. Both the acid dye and the basic dye preferably contain a xanthene-based basic dye and / or a triarylmethane-based basic dye. That is, it is preferable that the acid dye and / or the basic dye contains a xanthene dye and / or a triarylmethane dye.
　塩基性染料は、カチオン部の分子量が、３００以上７００以下であることが好ましい。これを満たす塩基性染料を用いた造塩化合物は、残膜率を高くしつつ開口部残渣をより少なくできる。カチオン部の分子量は構造式から計算で求めることができる。 The basic dye preferably has a cation portion having a molecular weight of 300 or more and 700 or less. A salt-forming compound using a basic dye satisfying this can increase the residual film ratio and reduce the opening residue. The molecular weight of the cation part can be calculated from the structural formula.
　（Ｃ１）酸性染料と塩基性染料からなる造塩化合物は、３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長が、いずれも５００ｎｍ以上７００ｎｍ以下である、一種類以上の酸性染料と一種類以上の塩基性染料からなる造塩化合物を含有することが好ましい。また、酸性染料の３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長をλａ、塩基性染料の３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長をλｂとしたとき、λａが５００ｎｍ以上５８０ｎｍ未満の範囲のいずれかに存在し、λｂが５８０ｎｍ以上７００ｎｍ以下の範囲のいずれかに存在することが好ましく、またはλａが５８０ｎｍ以上７００ｎｍ以下の範囲のいずれかに存在し、λｂが５００ｎｍ以上５８０ｎｍ未満の範囲のいずれかに存在することが好ましい。また、前記λａとλｂの差の絶対値は、４０ｎｍ以上１５０ｎｍ以下であることがより好ましい。これらをそれぞれ満たす酸性染料及び塩基性染料を用いた造塩化合物は、硬化物の黒色度（ＯＤ値）をより高くできる。 (C1) The salt-forming compound composed of an acidic dye and a basic dye has one or more acidic dyes and one or more basics having a maximum absorption wavelength of 500 nm or more and 700 nm or less in the region of 350 nm or more and 700 nm or less. It is preferable to contain a salt-forming compound composed of a dye. When the maximum absorption wavelength of the acid dye in the region of 350 nm or more and 700 nm or less is λ a , and the maximum absorption wavelength of the basic dye in the region of 350 nm or more and 700 nm or less is λ b , λ a is in the range of 500 nm or more and less than 580 nm. It is preferably present in any of the ranges of 580 nm or more and 700 nm or less, or λ a is present in any of the ranges of 580 nm or more and 700 nm or less and λ b is 500 nm or more and less than 580 nm . It is preferably present in any of the ranges. Further, the absolute value of the difference between λ a and λ b is more preferably 40 nm or more and 150 nm or less. A salt-forming compound using an acid dye and a basic dye that satisfy each of these can increase the blackness (OD value) of the cured product.
　（Ｃ１）酸性染料と塩基性染料からなる造塩化合物を酸性染料及び塩基性染料に分離し、吸収波長を測定する際には、酸性染料及び塩基性染料の対イオンの影響は特にないが、酸性染料はナトリウムイオン、塩基性染料は塩化物イオン又は臭化物イオンで測定するものとする。 (C1) When the salt-forming compound composed of the acidic dye and the basic dye is separated into the acidic dye and the basic dye and the absorption wavelength is measured, there is no particular influence of the pair ion of the acidic dye and the basic dye. Acid dyes shall be measured with sodium ions, and basic dyes shall be measured with chloride ions or bromide ions.
　酸性染料と塩基性染料との造塩化合物は、公知の方法で合成できる。例えば、酸性染料の水溶液と塩基性染料の水溶液をそれぞれ調製し、両者を混合すると、酸性染料と塩基性染料との造塩化合物が生成する。これをろ過により回収することにより、該造塩化合物を得ることができる。得られた該造塩化合物は、６０～７０℃程度で乾燥することが好ましい。 The salt-forming compound of the acid dye and the basic dye can be synthesized by a known method. For example, when an aqueous solution of an acid dye and an aqueous solution of a basic dye are prepared and mixed, a salt-forming compound of the acid dye and the basic dye is produced. The salt-forming compound can be obtained by recovering this by filtration. The obtained salt-forming compound is preferably dried at about 60 to 70 ° C.
　＜（Ｃ２）非イオン性染料、（Ｃ３）顔料＞
　本発明の着色感光性樹脂組成物は、（Ｃ）着色剤として、更に、（Ｃ２）非イオン性染料及び／又は（Ｃ３）顔料を含有することが好ましい。中でも、（Ｃ２）非イオン性染料を含有することが好ましい。 <(C2) nonionic dye, (C3) pigment>
The colored photosensitive resin composition of the present invention preferably further contains (C2) a nonionic dye and / or (C3) a pigment as the (C) colorant. Above all, it is preferable to contain (C2) nonionic dye.
　（Ｃ２）非イオン性染料とは、酸性染料及び塩基性染料以外の染料であり、イオン性の構造を持たないものをいう。 (C2) Non-ionic dyes are dyes other than acid dyes and basic dyes and do not have an ionic structure.
　（Ｃ２）非イオン性染料としては、例えば、
Ｃ．Ｉ．ディスパースオレンジ５；Ｃ．Ｉ．ディスパースレッド５８；Ｃ．Ｉ．ディスパースブルー１６５；Ｃ．Ｉ．ソルベントレッド１８などのアゾ系非イオン性染料；
Ｃ．Ｉ．バットブルー４；Ｃ．Ｉ．ディスパースレッド２２、６０；Ｃ．Ｉ．ディスパースバイオレット２６，２８、３１；Ｃ．Ｉ．ディスパースブルー１４、５６、６０；Ｃ．Ｉ，ソルベントバイオレット１３、３１、３６；Ｃ．Ｉ．ソルベントブルー３５、３６、４５、６３、７８、８７、９７、１０４、１２２等のアントラキノン系非イオン性染料などが挙げられる。 Examples of the (C2) nonionic dye include, for example.
C. I. Disperse Orange 5; C.I. I. Disperse thread 58; C.I. I. Disperse Blue 165; C.I. I. Azo-based nonionic dyes such as Solvent Red 18;
C. I. Bat Blue 4; C.I. I. Disperse threads 22, 60; C.I. I. Disperse Violet 26, 28, 31; C.I. I. Disperse Blue 14, 56, 60; C.I. I, Solvent Violet 13, 31, 36; C.I. I. Examples thereof include anthraquinone-based nonionic dyes such as Solvent Blue 35, 36, 45, 63, 78, 87, 97, 104 and 122.
　中でも、（Ｃ２）非イオン性染料としては、硬化物の黒色度（ＯＤ値）を高くできる点で、アントラキノン系非イオン性染料を含有することが好ましい。 Among them, as the (C2) nonionic dye, it is preferable to contain an anthraquinone-based nonionic dye in that the blackness (OD value) of the cured product can be increased.
　（Ｃ３）顔料とは、染料以外の着色化合物であり、水や有機溶剤に不溶なものをいう。　　　 (C3) Pigment is a coloring compound other than a dye and is insoluble in water or an organic solvent. It was
　（Ｃ３）顔料としては、有機顔料または無機顔料が挙げられる。有機顔料としては、例えば、フタロシアニン系顔料、アントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、チオインジゴ系顔料、ジケトピロロピロール系顔料、スレン系顔料、インドリン系顔料、ベンゾフラノン系顔料、ペリレン系顔料、アニリン系顔料、アゾ系顔料、縮合アゾ系顔料、カーボンブラックなどが挙げられる。また、無機顔料としては、例えば、グラファイト若しくは銀スズ合金、又は、チタン、銅、鉄、マンガン、コバルト、クロム、ニッケル、亜鉛、カルシウム、若しくは銀などの金属における、微粒子、酸化物、複合酸化物、硫化物、硫酸塩、硝酸塩、炭酸塩、窒化物、炭化物、酸窒化物などが挙げられる。 Examples of the (C3) pigment include organic pigments and inorganic pigments. Examples of organic pigments include phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, slene pigments, indolin pigments, benzofuranone pigments, and perylene pigments. Examples thereof include aniline pigments, azo pigments, condensed azo pigments, and carbon black. Examples of the inorganic pigment include fine particles, oxides, and composite oxides in a graphite or silver-tin alloy, or a metal such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver. , Sulfates, sulfates, nitrates, carbonates, nitrides, carbides, oxynitrides and the like.
　顔料を用いる場合、用いる顔料は、必要に応じて、ロジン処理、酸性基処理、塩基性基処理などの表面処理が施されているものを使用してもよい。また、場合により分散剤とともに使用することができる。分散剤は、例えば、カチオン系、アニオン系、非イオン系、両性、シリコーン系、フッ素系の界面活性剤を挙げることができる。 When a pigment is used, the pigment to be used may be one that has been subjected to surface treatment such as rosin treatment, acid group treatment, and basic group treatment, if necessary. In some cases, it can be used together with a dispersant. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants.
　着色感光性樹脂組成物における、（Ｃ）着色剤の含有量は、（Ａ）アルカリ可溶性樹脂の１００質量部に対して、１０～７５質量部が好ましく、２０～５０質量部がより好ましい。（Ｃ）成分の含有量が１０質量部以上とすることで、対応する波長の光を吸収させることができる。また、７５質量部以下とすることで、開口部残渣を低減させることができる。 The content of the (C) colorant in the colored photosensitive resin composition is preferably 10 to 75 parts by mass, more preferably 20 to 50 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. When the content of the component (C) is 10 parts by mass or more, light of the corresponding wavelength can be absorbed. Further, by setting the content to 75 parts by mass or less, the residue of the opening can be reduced.
　また、（Ｃ）着色剤における、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物の含有量は、１０～９０質量部が好ましく、２０～５０質量部がより好ましい。この範囲内とすることで、開口部残渣をより低減させ、残膜率をより向上させることができる。 Further, the content of the salt-forming compound composed of the (C1) acid dye and the basic dye in the (C) colorant is preferably 10 to 90 parts by mass, more preferably 20 to 50 parts by mass. Within this range, the residue of the opening can be further reduced and the residual film ratio can be further improved.
　さらに、（Ｃ）着色剤における、（Ｃ２）非イオン性染料及び／又は（Ｃ３）顔料の含有量は、（Ｃ２）非イオン性染料の含有量と（Ｃ３）顔料の含有量を合わせて１０～９０質量部が好ましく、５０～８０質量部がより好ましい。この範囲内とすることで、開口部残渣をより低減させ、残膜率をより向上させることができる。 Further, the content of the (C2) nonionic dye and / or the (C3) pigment in the (C) colorant is 10 including the content of the (C2) nonionic dye and the content of the (C3) pigment. It is preferably up to 90 parts by mass, more preferably 50 to 80 parts by mass. Within this range, the residue of the opening can be further reduced and the residual film ratio can be further improved.
　＜（Ｃ４）その他着色剤＞
　本発明の着色感光性樹脂組成物は、上記（Ｃ１）酸性染料と塩基性染料からなる造塩化合物、（Ｃ２）非イオン性染料及び／又は（Ｃ３）顔料以外の着色剤を含有してもよい。このような着色剤は、染料、有機顔料、無機顔料が挙げられるが、目的に合わせて公知のものを含有することができる。 <(C4) Other colorants>
The colored photosensitive resin composition of the present invention may contain a colorant other than the salt-forming compound composed of the above (C1) acid dye and basic dye, (C2) nonionic dye and / or (C3) pigment. good. Examples of such a colorant include dyes, organic pigments, and inorganic pigments, but known ones can be contained according to the purpose.
　（Ｃ）着色剤としては、例えば、Ｓｕｍｉｌａｎ、Ｌａｎｙｌ材料（住友化学工業（株）製）、Ｏｒａｓｏｌ、Ｏｒａｃｅｔ、Ｆｉｌａｍｉｄ、Ｉｒｇａｓｐｅｒｓｅ、Ｚａｐｏｎ、Ｎｅｏｚａｐｏｎ、Ｎｅｐｔｕｎｅ、Ａｃｉｄｏｌ材料（ＢＡＳＦ（株）製）、Ｋａｙａｓｅｔ、Ｋａｙａｋａｌａｎ材料（日本化薬（株）製）、Ｏｉｌ　Ｃｏｌｏｒｓ、Ｖａｌｉｆａｓｔ　Ｃｏｌｏｒｓ、Ｗａｔｅｒ　Ｃｏｌｏｒｓ材料（オリエント化学工業（株）製）、Ｓａｖｉｎｙｌ、Ｓａｎｄｏｐｌａｓｔ、Ｐｏｌｙｓｙｎｔｈｒｅｎ、Ｌａｎａｓｙｎ材料（クラリアントケミカルズ（株）製）、Ａｉｚｅｎ　Ｓｐｉｌｏｎ材料（保土谷化学工業（株）製）、Ｐｌａｓｔ　Ｃｏｌｏｒ、Ｏｉｌ　Ｃｏｌｏｒ材料（有本化学工業（株）製）等を入手できるが、それらに限定されるものではない。 (C) Coloring agents include, for example, Sumilan, Lanyl material (manufactured by Sumitomo Chemical Co., Ltd.), Orasol, Oracet, Filamid, Oilasperse, Zapon, Neozapon, Neptune, Acidol material (manufactured by BASF Co., Ltd.), Kayaset, and the like. Kayakaran material (manufactured by Nippon Kayaku Co., Ltd.), Oil Colors, Varifast Colors, Water Colors material (manufactured by Orient Chemical Industry Co., Ltd.), Savinyl, Sandoplast, Polysinthren, Lanasin material (Clariant Chemical) Materials (manufactured by Hodoya Chemical Industry Co., Ltd.), Last Color, Oil Color materials (manufactured by Arimoto Chemical Industry Co., Ltd.), etc. can be obtained, but are not limited thereto.
　＜（Ｄ）熱発色性化合物＞
　本発明の着色感光性樹脂組成物は、（Ｄ）熱発色性化合物を含有することが好ましい。（Ｄ）熱発色性化合物は、加熱前は３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長が３５０ｎｍ以上７００ｎｍ以下の範囲になく、１２０℃以上での加熱により、３５０ｎｍ以上７００ｎｍ以下の領域において、最大吸収波長が３５０ｎｍ以上７００ｎｍ以下の範囲のいずれかに生じる（以下、「熱発色する」と呼ぶ場合がある。）化合物である。（Ｄ）熱発色性化合物を用いることにより、加熱処理後、３５０ｎｍ以上７００ｎｍ以下の透過率を大きく低下させることができる。（Ｄ）熱発色性化合物は、１２０℃以上での加熱により、３５０ｎｍ以上７００ｎｍ以下の領域において、最大吸収波長が３５０ｎｍ以上５００ｎｍ以下の範囲のいずれかに生じる化合物を含有することが好ましい。（Ｃ１）酸性染料と塩基性染料からなる造塩化合物の３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長が５００ｎｍ以上７００ｎｍ以下であることが好ましいため、その場合でも、（Ｄ）熱発色性化合物を組み合わせることで、可視光領域の広範囲の透過率を下げることができる。 <(D) Thermal color-developing compound>
The colored photosensitive resin composition of the present invention preferably contains (D) a thermochromic compound. (D) The thermochromic compound has a maximum absorption wavelength in the region of 350 nm or more and 700 nm or less before heating, and is not in the range of 350 nm or more and 700 nm or less. It is a compound having a wavelength in any range of 350 nm or more and 700 nm or less (hereinafter, may be referred to as “thermal color development”). (D) By using the thermochromic compound, the transmittance of 350 nm or more and 700 nm or less can be significantly reduced after the heat treatment. The thermochromic compound (D) preferably contains a compound that is generated in the region of 350 nm or more and 700 nm or less and has a maximum absorption wavelength of 350 nm or more and 500 nm or less by heating at 120 ° C. or higher. (C1) Since the maximum absorption wavelength of the salt-forming compound composed of the acidic dye and the basic dye in the region of 350 nm or more and 700 nm or less is preferably 500 nm or more and 700 nm or less, even in that case, the (D) thermochromic compound is combined. This makes it possible to reduce the transmittance over a wide range in the visible light region.
　（Ｄ）熱発色性化合物は、１８０℃より高温で熱発色する熱発色性化合物が好ましい。熱発色性化合物の熱発色温度が高いほど高温条件下での耐熱性に優れ、また長時間の紫外光及び可視光の照射により退色することが少なく耐光性に優れる。 (D) The heat-coloring compound is preferably a heat-coloring compound that develops heat at a temperature higher than 180 ° C. The higher the thermal color development temperature of the thermochromic compound, the better the heat resistance under high temperature conditions, and the less the color fades due to long-term irradiation with ultraviolet light and visible light, and the better the light resistance.
　（Ｄ）熱発色性化合物は、一般の感熱色素又は感圧色素であってもよいし、その他の化合物であってもよい。これらの熱発色性化合物は１２０℃以上の加熱処理時に系中に共存する酸性基の作用により、その化学構造や電荷状態を変化させることによって熱発色するもの、あるいは空気中の酸素の存在により１２０℃以上で熱酸化反応等を起こして熱発色するもの等が挙げられる。熱発色性化合物の骨格構造としては、トリアリールメタン骨格、ジアリールメタン骨格、フルオラン骨格、ビスラクトン骨格、フタリド骨格、キサンテン骨格、ローダミンラクタム骨格、フルオレン骨格、フェノチアジン骨格、フェノキサジン骨格、スピロピラン骨格等が挙げられる。具体的には、特開２００４－３２６０９４号公報に記載の化合物等が挙げられる。中でも、トリアリールメタン骨格を有する水酸基含有化合物は、熱発色温度が高く耐熱性に優れるため特に好ましい。これらは単独でもしくは混合して用いられる。なお、トリアリールメタン骨格を有する水酸基含有化合物は当該化合物にナフトキノンジアジドのスルホン酸をエステル結合させて、キノンジアジド化合物として用いてもよい。 (D) The thermochromic compound may be a general heat-sensitive dye or a pressure-sensitive dye, or may be another compound. These thermochromic compounds develop heat by changing their chemical structure and charge state due to the action of acidic groups coexisting in the system during heat treatment at 120 ° C or higher, or 120 due to the presence of oxygen in the air. Examples thereof include those that cause a thermal oxidation reaction or the like at a temperature of ° C or higher to develop a thermal color. Examples of the skeleton structure of the thermochromic compound include triarylmethane skeleton, diarylmethane skeleton, fluorane skeleton, bislactone skeleton, phthalide skeleton, xanthene skeleton, rhodamine lactam skeleton, fluorene skeleton, phenoxazine skeleton, phenoxazine skeleton, and spiropyran skeleton. Be done. Specific examples thereof include the compounds described in JP-A-2004-326094. Among them, a hydroxyl group-containing compound having a triarylmethane skeleton is particularly preferable because it has a high thermal color development temperature and excellent heat resistance. These may be used alone or in admixture. The hydroxyl group-containing compound having a triarylmethane skeleton may be used as a quinone diazide compound by ester-bonding a sulfonic acid of naphthoquinone diazide to the compound.
　本発明で用いる（Ｄ）熱発色性化合物の含有量は、（Ａ）アルカリ可溶性樹脂の１００質量部に対して、５～８０質量部が好ましく、特に１０～６０質量部が好ましい。（Ｄ）熱発色性化合物の含有量が５質量部以上であれば、硬化物の紫外可視光領域における透過率を低下させることができる。また（Ｄ）熱発色性化合物の含有量が８０質量部以下であれば、硬化物の耐熱性や強度を維持し、吸水率を低減することができる。 The content of the (D) thermochromic compound used in the present invention is preferably 5 to 80 parts by mass, particularly preferably 10 to 60 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. (D) When the content of the thermochromic compound is 5 parts by mass or more, the transmittance of the cured product in the ultraviolet visible light region can be reduced. Further, when the content of the (D) thermochromic compound is 80 parts by mass or less, the heat resistance and strength of the cured product can be maintained and the water absorption rate can be reduced.
　本発明の着色感光性樹脂組成物は、必要に応じて、（Ａ）アルカリ可溶性樹脂、（Ｂ）光酸発生剤、（Ｃ）着色剤、（Ｄ）熱発色性化合物以外の化合物として、熱架橋剤、フェノール性水酸基を有する化合物、密着改良剤、界面活性剤などの種々の公知の添加剤を含有してもよい。 The colored photosensitive resin composition of the present invention can be used as a compound other than (A) alkali-soluble resin, (B) photoacid generator, (C) colorant, and (D) thermochromic compound, if necessary. Various known additives such as a cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, and a surfactant may be contained.
　＜溶剤＞
　本発明の着色感光性樹脂組成物は、溶剤を含有してもよい。溶剤としては、Ｎ－メチル－２－ピロリドン、γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、１，３－ジメチル－２－イミダゾリジノン、Ｎ，Ｎ’－ジメチルプロピレン尿素、Ｎ，Ｎ‐ジメチルイソ酪酸アミド、メトキシ－Ｎ，Ｎ－ジメチルプロピオンアミドなどの極性の非プロトン性溶媒、テトラヒドロフラン、ジオキサン、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルなどのエーテル類、アセトン、メチルエチルケトン、ジイソブチルケトンなどのケトン類、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、プロピレングリコールモノメチルエーテルアセテート、３－メチル－３－メトキシブチルアセテートなどのエステル類、乳酸エチル、乳酸メチル、ジアセトンアルコール、３－メチル－３－メトキシブタノールなどのアルコール類、トルエン、キシレンなどの芳香族炭化水素類等が挙げられる。これらを２種以上含有してもよい。溶剤の含有量は、（Ａ）アルカリ可溶性樹脂の１００質量部に対して、組成物を溶解させるため、１００質量部以上含有することが好ましい。 <Solvent>
The colored photosensitive resin composition of the present invention may contain a solvent. As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2. -Polar aprotonic solvents such as imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate. Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, aromatic hydrocarbons such as toluene and xylene, and the like. Two or more of these may be contained. The content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition in 100 parts by mass of the (A) alkali-soluble resin.
　＜着色感光性樹脂組成物の製造方法＞
　次に、本発明の着色感光性樹脂組成物の製造方法について説明する。 <Manufacturing method of colored photosensitive resin composition>
Next, a method for producing the colored photosensitive resin composition of the present invention will be described.
　本発明の着色感光性樹脂組成物を構成する成分である、前記（Ａ）アルカリ可溶性樹脂、（Ｂ）光酸発生剤、（Ｃ）着色剤と、必要により（Ｄ）熱発色性化合物、熱架橋剤、フェノール性水酸基を有する化合物、密着改良剤、界面活性剤、溶剤などを混合することにより、着色感光性樹脂組成物を得ることができる。後述する本発明の着色感光性樹脂組成物膜の製造方法に供する着色感光性樹脂組成物は、溶剤を含有し、前記各成分を溶解させることが好ましい。かかる場合に溶解を促進する方法としては、加熱や攪拌が挙げられる。加熱する場合、加熱温度は着色感光性樹脂組成物の性能を損なわない範囲で設定することが好ましく、通常、室温～８０℃である。なお、本明細書において室温とは、２５℃とする。また、各成分を溶解する順序は特に限定されず、例えば、溶剤に対し溶解性の低い化合物から順次溶解させる方法などが挙げられる。攪拌する場合、回転数は着色感光性樹脂組成物の性能を損なわない範囲で設定することが好ましく、通常、２００ｒｐｍ～２０００ｒｐｍである。攪拌する場合でも必要に応じて加熱してもよく、通常、室温～８０℃である。また、界面活性剤や一部の密着改良剤など、撹拌溶解時に気泡を発生しやすい成分については、他の成分を溶解してから最後に添加することで、気泡の発生による他成分の溶解不良を防ぐことができる。 The (A) alkali-soluble resin, (B) photoacid generator, (C) colorant, and optionally (D) thermochromic compound, heat, which are components constituting the colored photosensitive resin composition of the present invention. A colored photosensitive resin composition can be obtained by mixing a cross-linking agent, a compound having a phenolic hydroxyl group, an adhesion improver, a surfactant, a solvent and the like. The colored photosensitive resin composition used in the method for producing a colored photosensitive resin composition film of the present invention, which will be described later, preferably contains a solvent and dissolves each of the above components. Examples of the method for promoting dissolution in such a case include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the colored photosensitive resin composition, and is usually room temperature to 80 ° C. In the present specification, the room temperature is 25 ° C. Further, the order of dissolving each component is not particularly limited, and examples thereof include a method of sequentially dissolving compounds having low solubility in a solvent. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the colored photosensitive resin composition, and is usually 200 rpm to 2000 rpm. It may be agitated or heated as needed, and is usually at room temperature to 80 ° C. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.
　得られた着色感光性樹脂組成物は、濾過フィルターを用いて濾過し、ゴミや粒子を除去することが好ましい。フィルター孔径は、例えば０．５μｍ、０．２μｍ、０．１μｍ、０．０５μｍ、０．０２μｍなどがあるが、これらに限定されない。濾過フィルターの材質には、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）、ナイロン（ＮＹ）、ポリテトラフルオロエチエレン（ＰＴＦＥ）などがあるが、ポリエチレンやナイロンが好ましい。また、着色感光性樹脂組成物中に有機顔料を含有する場合、これらの粒子径より大きな孔径の濾過フィルターを用いることが好ましい。 It is preferable that the obtained colored photosensitive resin composition is filtered using a filtration filter to remove dust and particles. The filter hole diameter is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, and the like, but is not limited thereto. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, but polyethylene and nylon are preferable. When the colored photosensitive resin composition contains an organic pigment, it is preferable to use a filtration filter having a pore size larger than these particle sizes.
　本発明の着色感光性樹脂組成物は、有機ＥＬ表示装置の画素分割層用であることが好ましい。 The colored photosensitive resin composition of the present invention is preferably for the pixel dividing layer of the organic EL display device.
　＜着色感光性樹脂組成物を硬化した硬化物＞
　本発明の着色感光性樹脂組成物を硬化した硬化物について説明する。
着色感光性樹脂組成物を硬化した硬化物は、上述した着色感光性樹脂組成物を基板等に塗布して加熱処理して硬化した硬化物である。加熱処理条件としては２００℃以上が好ましく、２５０℃以上がより好ましい。また加熱処理条件は、４００℃以下が好ましく、３５０℃以下がより好ましい。 <Cured product obtained by curing the colored photosensitive resin composition>
A cured product obtained by curing the colored photosensitive resin composition of the present invention will be described.
The cured product obtained by curing the colored photosensitive resin composition is a cured product obtained by applying the above-mentioned colored photosensitive resin composition to a substrate or the like and heat-treating the cured product. The heat treatment conditions are preferably 200 ° C. or higher, more preferably 250 ° C. or higher. The heat treatment conditions are preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
　本発明の着色感光性樹脂組成物を硬化した硬化物は、硬化物の黒色度（ＯＤ値）をより高くできる点で、膜厚１．０μｍ以上５．０μｍ以下であることが好ましく、３．５μｍ以上５．０μｍ以下であることがより好ましい。本発明の着色感光性樹脂組成物は十分なアルカリ可溶性を持ち、厚膜にしても残渣が少なく、パターンを十分に開口させることができる。 The cured product obtained by curing the colored photosensitive resin composition of the present invention preferably has a film thickness of 1.0 μm or more and 5.0 μm or less in that the blackness (OD value) of the cured product can be further increased. It is more preferably 5 μm or more and 5.0 μm or less. The colored photosensitive resin composition of the present invention has sufficient alkali solubility, and even if it is a thick film, there is little residue and the pattern can be sufficiently opened.
　また、硬化物の膜厚１μｍ当たりのＯＤ値は、０．５以上２．０以下であることが好ましい。例えば、（Ａ）アルカリ可溶性樹脂の１００質量部に対する、（Ｃ）着色剤の含有量を１２～７５質量部とし、また、（Ｃ）着色剤における、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物の含有量を、２５～１００質量部とすることで、硬化物を所望のＯＤ値とすることができる。 Further, the OD value per 1 μm of the cured product is preferably 0.5 or more and 2.0 or less. For example, the content of the (C) colorant is 12 to 75 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin, and the (C) colorant is composed of (C1) acid dye and basic dye. By setting the content of the salt-forming compound to 25 to 100 parts by mass, the cured product can have a desired OD value.
　さらに、硬化物の反射色度は、ＣＩＥ　Ｌａｂ色空間表示系において、ａ＊値が－３０以上３０以下であり、ｂ＊値が－３０以上３０以下であることが好ましい。例えば、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物において、３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長の差が４０ｎｍ以上８０ｎｍ以下である酸性染料および塩基性染料からなる造塩化合物を用いることで、硬化物を所望の反射色度とすることができる。ａ＊値およびｂ＊値がこの範囲にあることで、より黒色に近い硬化物となり、該硬化物を具備する表示装置をより高品位なものにできる。 Further, the reflected chromaticity of the cured product is preferably a * value of -30 or more and 30 or less, and b * value of -30 or more and 30 or less in the CIE Lab color space display system. For example, in (C1) a salt-forming compound composed of an acidic dye and a basic dye, a salt-forming compound composed of an acidic dye and a basic dye having a difference in maximum absorption wavelength of 40 nm or more and 80 nm or less in a region of 350 nm or more and 700 nm or less is used. This makes it possible to obtain the desired reflected chromaticity of the cured product. When the a * value and the b * value are in this range, the cured product is closer to black, and the display device provided with the cured product can be made of higher quality.
　＜着色感光性樹脂組成物を用いた硬化物の製造方法＞
　本発明の着色感光性樹脂組成物を用いた硬化物の製造方法について説明する。
硬化物の製造方法は、（１）上述した着色感光性樹脂組成物を、基板に塗布し塗膜を形成する工程、（２）上記塗膜を活性化学線を用いて露光し、露光した塗膜を得る工程、（３）上記露光した塗膜をアルカリ溶液を用いて現像し、現像した塗膜を得る工程、及び、（４）上記現像した塗膜を加熱して硬化物を得る工程をこの順に有する。 <Manufacturing method of cured product using colored photosensitive resin composition>
A method for producing a cured product using the colored photosensitive resin composition of the present invention will be described.
The method for producing the cured product is as follows: (1) a step of applying the above-mentioned colored photosensitive resin composition to a substrate to form a coating film, and (2) an exposure of the above-mentioned coating film using an active chemical line and exposing the coating film. The steps of obtaining a film, (3) developing the exposed coating film with an alkaline solution to obtain a developed coating film, and (4) heating the developed coating film to obtain a cured product. Have in this order.
　（１）着色感光性樹脂組成物の塗膜を形成する工程では、本発明の着色感光性樹脂組成物をスピンコート法、スリットコート法、ディップコート法、スプレーコート法、印刷法などで塗布し、着色感光性樹脂組成物の塗膜を得る。塗布に先立ち、着色感光性樹脂組成物を塗布する基材を予め前述した密着改良剤で前処理してもよい。例えば、密着改良剤をイソプロパノール、エタノール、メタノール、水、テトラヒドロフラン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、乳酸エチル、アジピン酸ジエチルなどの溶媒に０．５～２０質量％溶解させた溶液を用いて、基材表面を処理する方法が挙げられる。基材表面の処理方法としては、スピンコート、スリットダイコート、バーコート、ディップコート、スプレーコート、蒸気処理などの方法が挙げられる。塗膜を乾燥する工程では、製膜した塗膜を必要に応じて減圧乾燥処理を施し、その後、ホットプレート、オーブン、赤外線などを用いて、５０℃～１８０℃の範囲で１分間～数時間の熱処理を施すことで塗膜を得る。 (1) In the step of forming a coating film of the colored photosensitive resin composition, the colored photosensitive resin composition of the present invention is applied by a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method or the like. , To obtain a coating film of a colored photosensitive resin composition. Prior to coating, the substrate to which the colored photosensitive resin composition is applied may be pretreated with the above-mentioned adhesion improving agent in advance. For example, a solution in which the adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass is used. Then, a method of treating the surface of the base material can be mentioned. Examples of the method for treating the surface of the base material include methods such as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. In the step of drying the coating film, the formed coating film is subjected to a vacuum drying treatment as necessary, and then using a hot plate, an oven, infrared rays, etc., in the range of 50 ° C to 180 ° C for 1 minute to several hours. A coating film is obtained by applying the heat treatment of.
　次に、（２）上記塗膜を活性化学線を用いて露光し、露光した塗膜を得る工程について説明する。 Next, (2) a process of exposing the coating film with an active chemical line to obtain an exposed coating film will be described.
　上記塗膜に活性化学線を照射する（以下、露光という場合もある。）。このとき、必要に応じて所望のパターンを有するフォトマスクを介して露光してもよいし、レーザーなどで直接塗膜に露光してもよい。露光に用いられる活性化学線としては紫外線、可視光線、電子線、Ｘ線などがあるが、本発明では水銀灯のｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）を用いることが好ましい。 Irradiate the above coating film with active chemical rays (hereinafter, may be referred to as exposure). At this time, if necessary, the exposure may be performed through a photomask having a desired pattern, or the coating film may be directly exposed with a laser or the like. The active chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps can be used. preferable.
　次に、（３）露光した塗膜を、アルカリ溶液を用いて現像し、現像した塗膜を得る工程について説明する。 Next, (3) a process of developing the exposed coating film with an alkaline solution to obtain the developed coating film will be described.
　上記露光した塗膜を、アルカリ溶液を用いて現像し、塗膜の露光部を除去する。このときの現像液は、テトラメチルアンモニウムヒドロキシド、ジエタノールアミン、ジエチルアミノエタノール、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、トリエチルアミン、ジエチルアミン、メチルアミン、ジメチルアミン、酢酸ジメチルアミノエチル、ジメチルアミノエタノール、ジメチルアミノエチルメタクリレート、シクロヘキシルアミン、エチレンジアミン、ヘキサメチレンジアミンなどのアルカリ性を示す化合物の水溶液が好ましい。また場合によっては、これらのアルカリ水溶液にＮ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、γ－ブチロラクトン、ジメチルアクリルアミドなどの極性溶媒、メタノール、エタノール、イソプロパノールなどのアルコール類、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートなどのエステル類、シクロペンタノン、シクロヘキサノン、イソブチルケトン、メチルイソブチルケトンなどのケトン類などを１種又は２種以上添加してもよい。現像方式としては、スプレー、パドル、浸漬、超音波等の方式が可能である。 The exposed coating film is developed with an alkaline solution to remove the exposed portion of the coating film. The developing solution at this time was tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol. , Dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and other alkaline compounds are preferred. In some cases, these alkaline aqueous solutions may be mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added in one or more. As the developing method, a method such as spraying, paddle, dipping, ultrasonic wave or the like is possible.
　次に、現像によって形成したパターンを蒸留水にてリンス処理をすることが好ましい。ここでもエタノール、イソプロピルアルコールなどのアルコール類、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートなどのエステル類などを蒸留水に加えてリンス処理をしてもよい。 Next, it is preferable to rinse the pattern formed by development with distilled water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to distilled water for rinsing.
　次に、（４）現像した塗膜を加熱処理して硬化物を得る工程について説明する。 Next, (4) a process of heat-treating the developed coating film to obtain a cured product will be described.
　現像した塗膜を加熱処理にすることにより残留溶剤や耐熱性の低い成分を除去できるため、硬化物の耐熱性及び耐薬品性を向上させることができる。この加熱処理はある温度を選び、段階的に昇温するか、ある温度範囲を選び連続的に昇温しながら５分間～５時間実施する。例えば、２３０℃で６０分間加熱処理する方法などが挙げられる。本発明においての加熱処理条件としては２００℃以上が好ましく、２３０℃以上がより好ましい。また加熱処理条件は、４００℃以下が好ましく、３５０℃以下がより好ましい。 By heat-treating the developed coating film, residual solvent and components with low heat resistance can be removed, so that the heat resistance and chemical resistance of the cured product can be improved. This heat treatment is carried out for 5 minutes to 5 hours while selecting a certain temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. For example, a method of heat-treating at 230 ° C. for 60 minutes can be mentioned. The heat treatment conditions in the present invention are preferably 200 ° C. or higher, more preferably 230 ° C. or higher. The heat treatment conditions are preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
　＜表示装置＞
　本発明の表示装置は、上記着色感光性樹脂組成物を硬化した硬化物を具備する。
着色感光性樹脂組成物を硬化した硬化物は、ＴＦＴが形成された基板、駆動回路上の平坦化層、第一電極上の画素分割層及び表示素子、第二電極をこの順に有する表示装置の平坦化層や画素分割層に含まれる。かかる構成の表示装置としては、液晶表示装置や有機ＥＬ表示装置などが挙げられる。中でも、平坦化層や画素分割層に対して高耐熱性や低アウトガス性が要求される有機ＥＬ表示装置に好適に用いられ、画素分割層に特に好適に用いることができる。 <Display device>
The display device of the present invention comprises a cured product obtained by curing the colored photosensitive resin composition.
The cured product obtained by curing the colored photosensitive resin composition is a display device having a substrate on which a TFT is formed, a flattening layer on a drive circuit, a pixel dividing layer and a display element on the first electrode, and a second electrode in this order. It is included in the flattening layer and the pixel dividing layer. Examples of the display device having such a configuration include a liquid crystal display device and an organic EL display device. Above all, it is suitably used for an organic EL display device that requires high heat resistance and low outgassing properties for a flattening layer and a pixel dividing layer, and can be particularly preferably used for a pixel dividing layer.
　本発明の着色感光性樹脂組成物を硬化した硬化物は、平坦化層、画素分割層のいずれか一方のみに用いてもよいし、両方に用いてもよい。アクティブマトリックス型の表示装置は、ガラスなどの基板上にＴＦＴとＴＦＴの側方部に位置しＴＦＴと接続された配線とを有し、その上に凹凸を覆うようにして平坦化層を有し、さらに平坦化層上に表示素子が設けられている。表示素子と配線とは、平坦化層に形成されたコンタクトホールを介して接続される。 The cured product obtained by curing the colored photosensitive resin composition of the present invention may be used for only one of the flattening layer and the pixel dividing layer, or may be used for both. The active matrix type display device has a TFT and wiring located on the side of the TFT and connected to the TFT on a substrate such as glass, and has a flattening layer on the TFT so as to cover the unevenness. Further, a display element is provided on the flattening layer. The display element and the wiring are connected via a contact hole formed in the flattening layer.
　以下実施例等をあげて本発明を説明するが、本発明はこれらの例によって限定されるものではない。 Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples.
　（１）残膜率の評価
　実施例及び比較例で調製した着色感光性樹脂組成物（以下、ワニスと記す場合もある。）を、ＩＴＯをスパッタにより成膜したガラス基板（ジオマテック（株）製；以下、「ＩＴＯ基板」）上にスピンコーター（ＭＳ－Ａ１００；ミカサ社製）を用いてプリベーク後の膜厚が３．０μｍとなるようにスピンコートで塗布し、ブザーホットプレート（ＨＰＤ－３０００ＢＺＮ；アズワン社製）を用いて１２０℃で１２０秒間プリベークし、プリベーク膜を作製した。得られたプリベーク膜２．３８質量％のテトラメチルアンモニウム（ＴＭＡＨ）水溶液で所望の膜厚を得るべく６０秒間現像し、次いで純水でリンスし、現像膜を得た。 (1) Evaluation of Remaining Film Ratio A glass substrate (manufactured by Geomatec Co., Ltd.) in which the colored photosensitive resin composition (hereinafter, also referred to as varnish) prepared in Examples and Comparative Examples is formed by spattering ITO. (Hereinafter, "ITO substrate") is coated with a spin coater (MS-A100; manufactured by Mikasa) with a spin coat so that the film thickness after prebaking is 3.0 μm, and a buzzer hot plate (HPD-3000BZN) is applied. Prebaked at 120 ° C. for 120 seconds using (manufactured by AS ONE) to prepare a prebaked film. The obtained prebake film was developed with a 2.38% by mass tetramethylammonium (TMAH) aqueous solution for 60 seconds to obtain a desired film thickness, and then rinsed with pure water to obtain a developed film.
　プリベーク膜及び現像膜の膜厚を触針式プロファイラー（Ｐ－１５；ケーエルエー・テンコール社製）を用いて測定し、これらの値から残膜率を次式で求めた。
残膜率［％］　＝　（現像膜の膜厚）／（プリベーク膜の膜厚）×１００。 The film thicknesses of the pre-baked film and the developed film were measured using a stylus type profiler (P-15; manufactured by KLA Tencor Co., Ltd.), and the residual film ratio was determined from these values by the following formula.
Remaining film ratio [%] = (film thickness of developing film) / (film thickness of prebaked film) × 100.
　（２）開口部残渣の評価
　開口部残渣の評価は、実施例及び比較例で調製した着色感光性樹脂組成物からなる硬化物を画素分割層として有する有機ＥＬ表示装置の発光面積率により評価した。 (2) Evaluation of Opening Residue The evaluation of the opening residue was evaluated by the emission area ratio of an organic EL display device having a cured product made of the colored photosensitive resin composition prepared in Examples and Comparative Examples as a pixel dividing layer. ..
　図１（ａ）～（ｄ）に使用した基板の概略図を示す。まず、３８×４６ｍｍの無アルカリガラス基板１に、スパッタ法によりＩＴＯ透明導電膜１０ｎｍを基板全面に形成し、第一電極２としてエッチングした。また、同時に第二電極を取り出すため補助電極３も同時に形成した（図１（ａ））。得られた基板を“セミコクリーン”（登録商標）５６（商品名、フルウチ化学（株）製）で１０分間超音波洗浄してから、超純水で洗浄した。次にこの基板全面に、各実施例及び比較例で調製した感光性樹脂組成物をスピンコート法により塗布し、１００℃のホットプレート上で２分間プリベークした。この膜にフォトマスクを介してＵＶ露光した後、２．３８質量％水酸化テトラメチルアンモニウム水溶液で現像し、露光部分のみを溶解させた後、純水でリンスした。得られたパターンを、窒素雰囲気下２３０℃のオーブン中で６０分間キュアした。このようにして、幅７０μｍ、長さ２６０μｍの開口部が幅方向にピッチ１５５μｍ、長さ方向にピッチ４６５μｍで配置され、それぞれの開口部が第一電極を露出せしめる形状の画素分割層４を、基板有効エリアに限定して形成した（図１（ｂ））。なお、この開口部が最終的に発光画素となる。また、基板有効エリアは１６ｍｍ四方、絶縁層の厚さは約１．０μｍであった。 The schematic diagram of the substrate used in FIGS. 1 (a) to 1 (d) is shown. First, an ITO transparent conductive film of 10 nm was formed on the entire surface of a 38 × 46 mm non-alkali glass substrate 1 by a sputtering method, and etched as a first electrode 2. In addition, an auxiliary electrode 3 was also formed at the same time in order to take out the second electrode at the same time (FIG. 1 (a)). The obtained substrate was ultrasonically cleaned with "Semicoclean" (registered trademark) 56 (trade name, manufactured by Furuuchi Chemical Co., Ltd.) for 10 minutes, and then washed with ultrapure water. Next, the photosensitive resin compositions prepared in each Example and Comparative Example were applied to the entire surface of this substrate by a spin coating method, and prebaked on a hot plate at 100 ° C. for 2 minutes. The film was UV-exposed via a photomask, then developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution, only the exposed portion was dissolved, and then rinsed with pure water. The resulting pattern was cured in an oven at 230 ° C. under a nitrogen atmosphere for 60 minutes. In this way, the pixel dividing layer 4 having an opening having a width of 70 μm and a length of 260 μm is arranged at a pitch of 155 μm in the width direction and a pitch of 465 μm in the length direction, and each opening exposes the first electrode. It was formed only in the effective area of the substrate (FIG. 1 (b)). It should be noted that this opening finally becomes a light emitting pixel. The effective area of the substrate was 16 mm square, and the thickness of the insulating layer was about 1.0 μm.
　次に、第一電極２、補助電極３、画素分割層４を形成した基板を用いて有機ＥＬ表示装置の作製を行った。前処理として窒素プラズマ処理をおこなった後、真空蒸着法により発光層を含む有機ＥＬ層５を形成した（図１（ｃ））。なお、蒸着時の真空度は１×１０－３Ｐａ以下であり、蒸着中は蒸着源に対して基板を回転させた。まず、正孔注入層として化合物（ＨＴ－１）を１０ｎｍ、正孔輸送層として化合物（ＨＴ－２）を５０ｎｍ蒸着した。次に発光層に、ホスト材料としての化合物（ＧＨ－１）とドーパント材料としての化合物（ＧＤ－１）を、ドープ濃度が１０％になるようにして４０ｎｍの厚さに蒸着した。次に、電子輸送材料として化合物（ＥＴ－１）と（ＬｉＱ）を体積比１：１で４０ｎｍの厚さに積層した。有機ＥＬ層で用いた化合物の構造を以下に示す。 Next, an organic EL display device was manufactured using a substrate on which the first electrode 2, the auxiliary electrode 3, and the pixel dividing layer 4 were formed. After performing nitrogen plasma treatment as a pretreatment, an organic EL layer 5 including a light emitting layer was formed by a vacuum vapor deposition method (FIG. 1 (c)). The degree of vacuum during vapor deposition was 1 × 10 -3 Pa or less, and the substrate was rotated with respect to the vapor deposition source during vapor deposition. First, the compound (HT-1) was deposited at 10 nm as the hole injection layer, and the compound (HT-2) was deposited at 50 nm as the hole transport layer. Next, a compound as a host material (GH-1) and a compound as a dopant material (GD-1) were deposited on the light emitting layer to a thickness of 40 nm so that the doping concentration was 10%. Next, the compound (ET-1) and (LiQ) were laminated as electron transport materials at a volume ratio of 1: 1 to a thickness of 40 nm. The structure of the compound used in the organic EL layer is shown below.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　次に、化合物（ＬｉＱ）を２ｎｍ蒸着した後、ＭｇＡｇを体積比１０：１で１０ｎｍ蒸着して第二電極６とした（図１（ｄ））。最後に、低湿窒素雰囲気下でエポキシ樹脂系接着剤を用いてキャップ状ガラス板を接着することで封止をし、１枚の基板上に５ｍｍ四方の発光装置を４つ作製した。なお、ここで言う膜厚は水晶発振式膜厚モニター表示値である。 Next, after depositing the compound (LiQ) at 2 nm, MgAg was vapor-deposited at a volume ratio of 10: 1 at 10 nm to obtain the second electrode 6 (FIG. 1 (d)). Finally, the cap-shaped glass plate was sealed by adhering the cap-shaped glass plate with an epoxy resin adhesive under a low humidity nitrogen atmosphere, and four 5 mm square light emitting devices were manufactured on one substrate. The film thickness referred to here is a crystal oscillation type film thickness monitor display value.
　上述の方法で作製した有機ＥＬ表示装置を１０ｍＡ／ｃｍ２で直流駆動にて発光させ、発光している領域の面積を測定し、発光面積率を以下の式により求めた。この値から、開口部残渣を以下のように判定した。
発光面積率［％］　＝　発光している領域の面積／発光画素の面積×１００
Ｓ：発光面積率が９５％以上１００％以下
Ａ：発光面積率が９０％以上９５％未満
Ｂ：発光面積率が７５％以上９０％未満
Ｃ：発光面積率が７５％未満。 The organic EL display device manufactured by the above method was made to emit light at 10 mA / cm 2 by direct current drive, the area of the light emitting region was measured, and the light emitting area ratio was calculated by the following formula. From this value, the opening residue was determined as follows.
Emission area ratio [%] = Area of emission area / Area of emission pixels x 100
S: Emission area ratio is 95% or more and 100% or less A: Emission area ratio is 90% or more and less than 95% B: Emission area ratio is 75% or more and less than 90% C: Emission area ratio is less than 75%.
　（３）黒色度（ＯＤ値）の評価
　５センチ角のガラス基板上にワニスを加熱処理（キュア）後の膜厚が１．５μｍとなるようにスピンコートで塗布し、１２０℃で１２０秒間プリベークし、プリベーク膜を作製した。その後、光洋サーモシステム（株）製高温クリーンオーブンＩＮＨ－９ＣＤ－Ｓを用いて、大気雰囲気下２３０℃で６０分間キュアし、耐熱性着色樹脂膜（硬化物）を作製した。なお、耐熱性着色樹脂膜（硬化物）の膜厚は、触針式プロファイラーを用いて測定した。このようにして得られた耐熱性着色樹脂膜（硬化物）について、光学濃度計（３６１ＴＶｉｓｕａｌ；Ｘ－Ｒｉｔｅ社製）を用いて、ＯＤ値を測定した。 (3) Evaluation of blackness (OD value) Apply varnish on a 5 cm square glass substrate with a spin coat so that the film thickness after heat treatment (cure) is 1.5 μm, and prebake at 120 ° C for 120 seconds. Then, a prebake film was prepared. Then, using a high-temperature clean oven INH-9CD-S manufactured by Koyo Thermo System Co., Ltd., the mixture was cured at 230 ° C. for 60 minutes in an air atmosphere to prepare a heat-resistant colored resin film (cured product). The film thickness of the heat-resistant colored resin film (cured product) was measured using a stylus type profiler. The OD value of the heat-resistant colored resin film (cured product) thus obtained was measured using an optical densitometer (361TVisual; manufactured by X-Rite).
　なお、キュア膜の膜厚が１．５μｍでなかった場合には、膜厚を１．５μｍとした場合の光透過率に換算した。 When the film thickness of the cure film was not 1.5 μm, it was converted into the light transmittance when the film thickness was 1.5 μm.
　（４）反射色度の評価
　前記（３）黒色度（ＯＤ値）の評価において、基板として５センチ角のガラス基板の代わりに、ＩＴＯ／Ａｇ（１０ｎｍ／１００ｎｍ）が製膜された５センチ角のガラス基板（ジオマテック（株）製）を用いた以外は同様の手法で、耐熱性着色樹脂膜（硬化物）を作製し、分光測色計（ＣＭ－２６００ｄ；コニカミノルタ社製）を用いて、正反射光込み（ＳＣＩ方式）の反射色度ａ＊およびｂ＊を測定した。 (4) Evaluation of Reflective Color In the evaluation of (3) Blackness (OD value), ITO / Ag (10 nm / 100 nm) was formed into a 5 cm square instead of a 5 cm square glass substrate. A heat-resistant colored resin film (cured product) was prepared by the same method except that the glass substrate (manufactured by Geomatec Co., Ltd.) was used, and a spectrocolorimeter (CM-2600d; manufactured by Konica Minolta) was used. , Reflected chromaticity a * and b * including specular reflected light (SCI method) were measured.
　［合成例１］
　三口フラスコに、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン（セントラル硝子（株）製、以下、ＢＡＨＦ）１８．３１ｇ（０．０５ｍｏｌ）、プロピレンオキシド（東京化成工業（株）製）１７．４ｇ（０．３ｍｏｌ）、アセトン１００ｍＬを秤量して溶解させた。ここに、アセトン１０ｍＬに塩化３－ニトロベンゾイル（東京化成工業（株）製）２０．４１ｇ（０．１１ｍｏｌ）を溶かした溶液を滴下した。滴下終了後、－１５℃で４時間反応させ、その後室温に戻した。析出した白色固体をろ取し、５０℃で真空乾燥させた。得られた固体３０ｇを、３００ｍＬのステンレスオートクレーブに入れ、２－メトキシエタノール２５０ｍＬに分散させ、５％パラジウム－炭素（富士フイルム和光純薬（株）製）を２ｇ加えた。ここに水素を風船で導入して、室温で２時間反応させた。２時間後、風船がこれ以上しぼまないことを確認した。反応終了後、ろ過して触媒であるパラジウム化合物を除去し、減圧留去させて濃縮し、下記構造のヒドロキシ基含有ジアミン化合物（ＨＡ）を得た。 [Synthesis Example 1]
In a three-necked flask, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter BAHF) 18.31 g (0.05 mol), propylene oxide (Tokyo Chemical Industry Co., Ltd. (Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) 17.4 g (0.3 mol) and 100 mL of acetone were weighed and dissolved. A solution prepared by dissolving 20.41 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 10 mL of acetone was added dropwise thereto. After completion of the dropping, the reaction was carried out at −15 ° C. for 4 hours, and then the temperature was returned to room temperature. The precipitated white solid was collected by filtration and vacuum dried at 50 ° C. 30 g of the obtained solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of 2-methoxyethanol, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and reacted at room temperature for 2 hours. After 2 hours, I confirmed that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration, distilled off under reduced pressure, and concentrated to obtain a hydroxy group-containing diamine compound (HA) having the following structure.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　乾燥窒素気流下、ＨＡ１５．１ｇ（０．０２５モル）、ＢＡＨＦ３．６６ｇ（０．０１モル）及び１，３－ビス（３－アミノプロピル）テトラメチルジシロキサン（以下、ＳｉＤＡ）０．６２ｇ（０．００２５モル）をＮ－メチルピロリドン（ＮＭＰ）２００ｇに溶解した。ここに２，２－（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン（以下、６ＦＤＡ）２２．２ｇ（０．０５モル）をＮＭＰ５０ｇとともに加えて、４０℃で１時間撹拌した。その後、３－アミノフェノール（東京化成工業（株）製、以下、ＭＡＰ）２．７３ｇ（０．０２５モル）を加え、４０℃で１時間撹拌した。さらに、Ｎ，Ｎ－ジメチルホルムアミドジメチルアセタール（三菱レーヨン（株）製、以下、ＤＦＡ）１１．９ｇ（０．１モル）をＮＭＰ５ｇで希釈した溶液を投入後、４０℃で２時間撹拌を続けた。撹拌終了後、溶液を水２Ｌに投入して、ポリマー固体の沈殿をろ過で集めた。さらに水２Ｌで３回洗浄を行い、集めたポリマー固体を５０℃の真空乾燥機で７２時間乾燥し、（Ａ）アルカリ可溶性樹脂としてポリイミド前駆体樹脂ａ－１を得た。 Under a dry nitrogen stream, HA15.1 g (0.025 mol), BAHF 3.66 g (0.01 mol) and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) 0.62 g (0) .0025 mol) was dissolved in 200 g of N-methylpyrrolidone (NMP). To this, 22.2 g (0.05 mol) of 2,2- (3,4-dicarboxyphenyl) hexafluoropropane (hereinafter, 6FDA) was added together with 50 g of NMP, and the mixture was stirred at 40 ° C. for 1 hour. Then, 2.73 g (0.025 mol) of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter MAP) was added, and the mixture was stirred at 40 ° C. for 1 hour. Further, a solution obtained by diluting 11.9 g (0.1 mol) of N, N-dimethylformamide dimethylacetal (manufactured by Mitsubishi Rayon Co., Ltd., hereinafter, DFA) with 5 g of NMP was added, and then stirring was continued at 40 ° C. for 2 hours. .. After the stirring was completed, the solution was poured into 2 L of water and the precipitate of the polymer solid was collected by filtration. Further, the polymer solid was washed 3 times with 2 L of water and dried in a vacuum dryer at 50 ° C. for 72 hours to obtain (A) a polyimide precursor resin a-1 as an alkali-soluble resin.
　［合成例２］
　乾燥窒素気流下、４，４’－［１－［４－［１－（４－ヒドロキシフェニル－１）－１－メチルエチル］フェニル］エチリデン］ビスフェノール（ＴｒｉｓＰ－ＰＡ、本州化学工業（株）製）、４２．４ｇ（０．１モル）と５－ナフトキノンジアジドスルホン酸クロリド（東洋合成（株）製）７２．３ｇ（０．２７モル）を１，４－ジオキサン４５０ｇに溶解させ、室温にした。ここに、１，４－ジオキサン１００ｇと混合したトリエチルアミン２５．０ｇを、系内が３５℃以上にならないように滴下した。滴下後、４０℃で２時間撹拌した。トリエチルアミン塩を濾過し、濾液を水に投入した。その後、析出した沈殿を濾過で集め、さらに１％塩酸水１Ｌで洗浄した。その後、さらに水２Ｌで２回洗浄した。この沈殿を真空乾燥機で乾燥し、下記式で表されるキノンジアジド化合物ｂ－１を得た。 [Synthesis Example 2]
Under a dry nitrogen stream, 4,4'-[1- [4- [1- (4-hydroxyphenyl-1) -1-methylethyl] phenyl] ethylidene] bisphenol (TrisP-PA, manufactured by Honshu Chemical Industry Co., Ltd.) ), 42.4 g (0.1 mol) and 72.3 g (0.27 mol) of 5-naphthoquinone diazidosulfonic acid chloride (manufactured by Toyo Gosei Co., Ltd.) were dissolved in 1,4-dioxane (450 g) and brought to room temperature. .. Here, 25.0 g of triethylamine mixed with 100 g of 1,4-dioxane was added dropwise so that the temperature inside the system did not rise above 35 ° C. After the dropping, the mixture was stirred at 40 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was added to water. Then, the precipitated precipitate was collected by filtration and further washed with 1 L of 1% hydrochloric acid water. Then, it was further washed twice with 2 L of water. This precipitate was dried in a vacuum dryer to obtain a quinonediazide compound b-1 represented by the following formula.
　［合成例３］
　セパラブルフラスコに塩基性染料としてＣ．Ｉ．ベーシックブルー７（東京化成工業（株）製）　９．２５ｇ（０．０１８モル）、純水２００ｇを投入し、６０℃にて３０分攪拌した。酸性染料としてＣ．Ｉ．アシッドレッド５２（富士フイルム和光純薬（株）製）　１１．５０ｇ（０．０１９．８モル）を純水１２０ｇに溶解させた水溶液を投入後、６０℃にて６０分攪拌した。その後、室温まで冷却後、反応液をろ過し、紫色の固体を得た。この固体を６０℃で８時間乾燥させ、造塩化合物ｃ１－１を得た。 [Synthesis Example 3]
As a basic dye in a separable flask, C.I. I. Basic Blue 7 (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.25 g (0.018 mol) and 200 g of pure water were added, and the mixture was stirred at 60 ° C. for 30 minutes. As an acid dye, C.I. I. An aqueous solution prepared by dissolving 11.50 g (0.019.8 mol) of Acid Red 52 (manufactured by Wako Pure Chemical Industries, Ltd.) in 120 g of pure water was added, and the mixture was stirred at 60 ° C. for 60 minutes. Then, after cooling to room temperature, the reaction solution was filtered to obtain a purple solid. This solid was dried at 60 ° C. for 8 hours to obtain a salt-forming compound c1-1.
　［合成例４～１０］
合成例３と同様の手法で、塩基性染料及び酸性染料として表１に挙げた化合物を使用して造塩化合物ｃ１－２～ｃ１－８を得た。 [Synthesis Examples 4 to 10]
Salt-forming compounds c1-2 to c1-8 were obtained using the compounds listed in Table 1 as basic dyes and acid dyes in the same manner as in Synthesis Example 3.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　各実施例及び比較例に示した化合物を以下に示す。
（Ｃ２）非イオン性染料
ｃ２－１：Ｃ．Ｉ．ソルベントブルー４５
ｃ２－２：Ｃ．Ｉ．ソルベントブルー６３
ｃ２－３：Ｃ．Ｉ．ソルベントレッド１８
ｃ２－４：Ｃ．Ｉ．ディスパースバイオレット３１
（Ｃ３）顔料
ｃ３－１：Ｃ．Ｉ．ピグメントブルー６０
（Ｃ４）その他着色剤
ｃ４－１：Ｃ．Ｉ．アシッドレッド５２。 The compounds shown in each Example and Comparative Example are shown below.
(C2) Nonionic dye c2-1: C.I. I. Solvent blue 45
c2-2: C.I. I. Solvent blue 63
c2-3: C.I. I. Solvent Red 18
c2-4: C.I. I. Disperse Violet 31
(C3) Pigment c3-1: C.I. I. Pigment Blue 60
(C4) Other colorants c4-1: C.I. I. Acid Red 52.
　（Ｂ）光酸発生剤ｂ－１、（Ｄ）熱発色性化合物ｄ－１、その他添加剤として、熱架橋剤ｅ－１、フェノール性水酸基を有する化合物ｆ－１、密着改良剤ｇ－１の構造を以下に示す。 (B) Photoacid generator b-1, (D) Thermal color-developing compound d-1, as other additives, thermal cross-linking agent e-1, compound f-1 having a phenolic hydroxyl group, adhesion improver g-1 The structure of is shown below.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　［実施例１］
黄色灯下、（Ａ）アルカリ可溶性樹脂として合成例１で得たポリイミド前駆体樹脂ａ－１、（Ｂ）光酸発生剤として合成例２で得た化合物ｂ－１、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物として合成例３で得た化合物ｃ１－１、（Ｃ２）非イオン性染料として化合物ｃ２－１、（Ｄ）熱発色性化合物として化合物ｄ－１、その他添加剤として熱架橋剤ｅ－１、フェノール性水酸基を有する化合物ｆ－１、密着改良剤ｇ－１、溶剤としてγ－ブチロラクトン（ＧＢＬ）及び乳酸エチル（ＥＬ）を１／１の質量比率で表１に示す量を添加し、攪拌して溶解させ、組成物１を調製した。 [Example 1]
Under yellow light, (A) the polyimide precursor resin a-1 obtained in Synthesis Example 1 as an alkali-soluble resin, (B) the compound b-1 obtained in Synthesis Example 2 as a photoacid generator, and (C1) an acidic dye. Compound c1-1 obtained in Synthesis Example 3 as a salt-forming compound composed of a basic dye, compound c2-1 as a nonionic dye, compound d-1 as a thermochromic compound, and other additives. Table 1 shows the thermal cross-linking agent e-1, the compound f-1 having a phenolic hydroxyl group, the adhesion improver g-1, γ-butyrolactone (GBL) and ethyl lactate (EL) as solvents in a mass ratio of 1/1. Amount was added and stirred to dissolve to prepare composition 1.
　組成物１について、残膜率、開口部残渣、ＯＤ値及び反射色度の評価を行った。 For composition 1, the residual film ratio, opening residue, OD value and reflected chromaticity were evaluated.
　［実施例２～１６、比較例１～３］
　実施例１と同様の手法で、組成物２～１９を表２に記載の組成にて調製した。 [Examples 2 to 16, Comparative Examples 1 to 3]
Compositions 2 to 19 were prepared with the compositions shown in Table 2 by the same method as in Example 1.
　実施例１と同様の手法で、組成物２～１９を評価した。評価結果を表３に示す。 Compositions 2 to 19 were evaluated by the same method as in Example 1. The evaluation results are shown in Table 3.
　［実施例１７］
　（Ａ）アルカリ可溶性樹脂として合成例１で得たポリイミド樹脂ａ－１　５０ｇ、（Ｃ３）顔料として化合物ｃ３－１　１００ｇ、およびγ－ブチロラクトン１０００ｇをタンクに仕込み、ホモミキサーで２０分撹拌し、予備分散液を得た。０．０５ｍｍφジルコニアビーズを７５体積％充填した遠心分離セパレーターを具備した（株）広島メタル＆マシナリー製分散機ウルトラアペックスミルに、得られた予備分散液を供給し、回転速度１０ｍ／ｓで３時間分散を行い、顔料分散液を得た。 [Example 17]
(A) 50 g of the polyimide resin a-1 obtained in Synthesis Example 1 as an alkali-soluble resin, 100 g of the compound c3-1 as a pigment (C3), and 1000 g of γ-butyrolactone were charged in a tank, and the mixture was stirred with a homomixer for 20 minutes to prepare. A dispersion was obtained. The obtained pre-dispersion liquid was supplied to the Ultra Apex Mill, a disperser manufactured by Hiroshima Metal & Machinery Co., Ltd., equipped with a centrifuge separator filled with 75% by volume of 0.05 mmφ zirconia beads, and the rotation speed was 10 m / s for 3 hours. Dispersion was carried out to obtain a pigment dispersion liquid.
　この顔料分散液４．５ｇと、（Ａ）アルカリ可溶性樹脂として合成例１で得たポリイミド樹脂ａ－１　３．２８ｇ、（Ｂ）光酸発生剤として合成例２で得た化合物ｂ－１　１．０ｇ、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物として合成例３で得た化合物ｃ１－１　０．３５ｇ、（Ｄ）熱発色性化合物として化合物ｄ－１　０．７ｇ、その他添加剤として熱架橋剤ｅ－１　０．６ｇ、フェノール性水酸基を有する化合物ｆ－１　０．４ｇ、密着改良剤ｇ－１　０．１ｇ、溶剤としてγ－ブチロラクトン（ＧＢＬ）　５．５ｇ、及び乳酸エチル（ＥＬ）　１０ｇを混合し、攪拌して溶解させ、組成物２０を調製した。 4.5 g of this pigment dispersion, 3.28 g of the polyimide resin a-1 obtained in Synthesis Example 1 as (A) an alkali-soluble resin, and (B) compound b-1 1 obtained in Synthesis Example 2 as a photoacid generator. 0.0 g, (C1) 0.35 g of the compound c1-1 obtained in Synthesis Example 3 as a salt-forming compound composed of an acidic dye and a basic dye, 0.7 g of the compound d-1 as a (D) thermochromic compound, and others added. Thermal cross-linking agent e-1 0.6 g, compound f-1 having phenolic hydroxyl group 0.4 g, adhesion improver g-1 0.1 g, γ-butyrolactone (GBL) 5.5 g as solvent, and ethyl lactate. (EL) 10 g was mixed, stirred and dissolved to prepare the composition 20.
　実施例１と同様の手法で、組成物２０を評価した。評価結果を表３に示す。 The composition 20 was evaluated by the same method as in Example 1. The evaluation results are shown in Table 3.
　［実施例１８］
　実施例２において、（２）開口部残渣の評価を絶縁層の厚さが３．５μｍとなるように、及び（３）黒色度（ＯＤ値）及び（４）反射式度の評価を耐熱性着色樹脂膜（硬化物）の厚さが３．５μｍとなるように実施した以外は同様の手法で、組成物２を評価した。評価結果を表３に示す。 [Example 18]
In Example 2, (2) evaluation of the opening residue was made so that the thickness of the insulating layer was 3.5 μm, and (3) blackness (OD value) and (4) evaluation of the degree of reflection were heat resistance. The composition 2 was evaluated by the same method except that the thickness of the colored resin film (cured product) was 3.5 μm. The evaluation results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　上記結果より、本発明による着色感光性樹脂組成物は、残膜率、開口部残渣、および黒色度の特性を両立してパターンを形成できることが確認された。 From the above results, it was confirmed that the colored photosensitive resin composition according to the present invention can form a pattern while achieving both the characteristics of residual film ratio, opening residue, and blackness.
１：ガラス基板
２：第一電極
３：補助電極
４：画素分割層
５：有機ＥＬ層
６：第二電極
  1: Glass substrate 2: First electrode 3: Auxiliary electrode 4: Pixel dividing layer 5: Organic EL layer 6: Second electrode

Claims (22)

  1. （Ａ）アルカリ可溶性樹脂、（Ｂ）光酸発生剤、（Ｃ）着色剤を含有する着色感光性樹脂組成物であって、該（Ｃ）着色剤が、（Ｃ１）酸性染料と塩基性染料からなる造塩化合物を含有する、着色感光性樹脂組成物。 A colored photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photoacid generator, and (C) a colorant, wherein the (C) colorant is (C1) an acid dye and a basic dye. A colored photosensitive resin composition containing a salt-forming compound comprising.
  2. 前記（Ｃ１）酸性染料と塩基性染料からなる造塩化合物が、３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長が、いずれも５００ｎｍ以上７００ｎｍ以下である、一種類以上の酸性染料と一種類以上の塩基性染料からなる造塩化合物を含有する、請求項１に記載の着色感光性樹脂組成物。 One or more acid dyes and one or more bases in which the salt-forming compound composed of the (C1) acid dye and the basic dye has a maximum absorption wavelength of 500 nm or more and 700 nm or less in the region of 350 nm or more and 700 nm or less. The colored photosensitive resin composition according to claim 1, which contains a salt-forming compound made of an acid dye.
  3. 前記着色感光性樹脂組成物が、有機ＥＬ表示装置の画素分割層用である、請求項１または２に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 1 or 2, wherein the colored photosensitive resin composition is for a pixel dividing layer of an organic EL display device.
  4. 前記酸性染料をナトリウム塩としたときの、２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液への溶解度が、４質量％以上９質量％以下である、請求項１～３のいずれかに記載の着色感光性樹脂組成物。 The coloring according to any one of claims 1 to 3, wherein the solubility in a 2.38% by mass tetramethylammonium hydroxide aqueous solution when the acid dye is a sodium salt is 4% by mass or more and 9% by mass or less. Photosensitive resin composition.
  5. 前記酸性染料のアニオン部の酸性基の数が、前記酸性染料におけるアニオン部の分子量１０００あたり、２以上６以下である、請求項１～４のいずれかに記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the number of acidic groups in the anion portion of the acid dye is 2 or more and 6 or less per 1000 molecular weight of the anion portion in the acid dye.
  6. 前記塩基性染料において、カチオン部の分子量が、３００以上７００以下である、請求項１～５のいずれかに記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 5, wherein the basic dye has a molecular weight of 300 or more and 700 or less.
  7. 前記酸性染料の３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長をλａ、前記塩基性染料の３５０ｎｍ以上７００ｎｍ以下の領域における最大吸収波長をλｂとしたとき、λａが５００ｎｍ以上５８０ｎｍ未満の範囲のいずれかに存在し、λｂが５８０ｎｍ以上７００ｎｍ以下の範囲のいずれかに存在する、またはλａが５８０ｎｍ以上７００ｎｍ以下の範囲のいずれかに存在し、λｂが５００ｎｍ以上５８０ｎｍ未満の範囲のいずれかに存在する請求項１～６のいずれかに記載の着色感光性樹脂組成物。 When the maximum absorption wavelength of the acid dye in the region of 350 nm or more and 700 nm or less is λ a , and the maximum absorption wavelength of the basic dye in the region of 350 nm or more and 700 nm or less is λ b , λ a is in the range of 500 nm or more and less than 580 nm. Any of the following, λ b is present in any of the range of 580 nm or more and 700 nm or less, or λ a is present in any of the range of 580 nm or more and 700 nm or less, and λ b is present in any of the range of 500 nm or more and less than 580 nm. The colored photosensitive resin composition according to any one of claims 1 to 6, which is present in the above.
  8. 前記λａと前記λｂの差の絶対値が、４０ｎｍ以上１５０ｎｍ以下である、請求項７に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 7, wherein the absolute value of the difference between λ a and λ b is 40 nm or more and 150 nm or less.
  9. 更に、（Ｄ）熱発色性化合物を含有する、請求項１～８のいずれかに記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 8, further comprising (D) a thermochromic compound.
  10. 前記（Ｄ）熱発色性化合物が、１２０℃以上の加熱により、３５０ｎｍ以上７００ｎｍ以下の領域において、最大吸収波長が３５０ｎｍ以上５００ｎｍ以下の範囲のいずれかに生じる化合物を含有する、請求項９に記載の着色感光性樹脂組成物。 The ninth aspect of the present invention, wherein the thermochromic compound (D) contains a compound produced by heating at 120 ° C. or higher in a region of 350 nm or more and 700 nm or less, in which the maximum absorption wavelength is in the range of 350 nm or more and 500 nm or less. Colored photosensitive resin composition.
  11. 前記（Ａ）アルカリ可溶性樹脂が、ポリイミド、ポリイミド前駆体、ポリベンゾオキサゾール、ポリベンゾオキサゾール前駆体及びそれらの共重合体からなる群より選択される一種類以上を含有する、請求項１～１０のいずれかに記載の着色感光性樹脂組成物。 Claims 1 to 10 wherein the alkali-soluble resin (A) contains at least one selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor and a copolymer thereof. The colored photosensitive resin composition according to any one.
  12. 前記酸性染料及び／又は前記塩基性染料が、キサンテン系染料及び／又はトリアリールメタン系染料を含有する、請求項１～１１のいずれかに記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 11, wherein the acid dye and / or the basic dye contains a xanthene dye and / or a triarylmethane dye.
  13. 更に、（Ｃ２）非イオン性染料及び／又は（Ｃ３）顔料を含有する、請求項１～１２のいずれかに記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 12, further comprising (C2) a nonionic dye and / or (C3) a pigment.
  14. 前記（Ｃ２）非イオン性染料を含有し、前記（Ｃ２）非イオン性染料が、アントラキノン系非イオン性染料を含有する、請求項１３に記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to claim 13, wherein the (C2) non-ionic dye is contained, and the (C2) non-ionic dye contains an anthraquinone-based non-ionic dye.
  15. 前記（Ｃ）着色剤の含有比率が、前記（Ａ）アルカリ可溶性樹脂１００質量部に対して、１０～７５質量部である、請求項１～１４のいずれかに記載の着色感光性樹脂組成物。 The colored photosensitive resin composition according to any one of claims 1 to 14, wherein the content ratio of the (C) colorant is 10 to 75 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. ..
  16. 請求項１～１５のいずれかに記載の着色感光性樹脂組成物を硬化した硬化物。 A cured product obtained by curing the colored photosensitive resin composition according to any one of claims 1 to 15.
  17. 前記硬化物の膜厚が、１．０μｍ以上５．０μｍ以下である、請求項１６に記載の硬化物。 The cured product according to claim 16, wherein the cured product has a film thickness of 1.0 μm or more and 5.0 μm or less.
  18. 前記硬化物の膜厚が、３．５μｍ以上５．０μｍ以下である、請求項１６または１７に記載の硬化物。 The cured product according to claim 16 or 17, wherein the cured product has a film thickness of 3.5 μm or more and 5.0 μm or less.
  19. 前記硬化物の膜厚１μｍあたりのＯＤ値が０．５以上２．０以下である、請求項１６～１８のいずれかに記載の硬化物。 The cured product according to any one of claims 16 to 18, wherein the OD value per 1 μm of the cured product is 0.5 or more and 2.0 or less.
  20. 前記硬化物の反射色度が、ＣＩＥ　Ｌａｂ色空間表示系においてａ＊値が－３０以上３０以下であり、ｂ＊値が－３０以上３０以下である、請求項１６～１９のいずれかに記載の硬化物。 16 . Hardened product.
  21. 請求項１６～２０のいずれかに記載の硬化物を具備する表示装置。 A display device comprising the cured product according to any one of claims 16 to 20.
  22. （１）請求項１～１５のいずれかに記載の着色感光性樹脂組成物を基板に塗布して塗膜を形成する工程、
    （２）該塗膜を活性化学線を用いて露光し、露光した塗膜を得る工程、
    （３）該露光した塗膜を、アルカリ溶液を用いて現像し、現像した塗膜を得る工程、及び、
    （４）該現像した塗膜を加熱して、硬化物を得る工程、
    をこの順に有する硬化物の製造方法。
          (1) A step of applying the colored photosensitive resin composition according to any one of claims 1 to 15 to a substrate to form a coating film.
    (2) A step of exposing the coating film with an active chemical line to obtain an exposed coating film.
    (3) A step of developing the exposed coating film with an alkaline solution to obtain a developed coating film, and
    (4) A step of heating the developed coating film to obtain a cured product.
    A method for producing a cured product having the above in this order.
PCT/JP2021/029076 2020-08-18 2021-08-05 Colored photosensitive resin composition, cured object, display device, and method for producing cured object WO2022039034A1 (en)

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