WO2022039034A1 - 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 - Google Patents

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 Download PDF

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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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English (en)
French (fr)
Japanese (ja)
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西岡拓紀
小森悠佑
三好一登
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Toray Industries Inc
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Toray Industries Inc
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Priority to JP2021546701A priority Critical patent/JP7750093B2/ja
Priority to CN202180056116.5A priority patent/CN116034318A/zh
Priority to KR1020227040798A priority patent/KR102903882B1/ko
Publication of WO2022039034A1 publication Critical patent/WO2022039034A1/ja
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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.

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PCT/JP2021/029076 2020-08-18 2021-08-05 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 Ceased WO2022039034A1 (ja)

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