WO2021149410A1 - ポジ型感光性樹脂組成物、硬化膜、積層体、導電パターン付き基板、積層体の製造方法、タッチパネル及び有機ｅｌ表示装置 - Google Patents

ポジ型感光性樹脂組成物、硬化膜、積層体、導電パターン付き基板、積層体の製造方法、タッチパネル及び有機ｅｌ表示装置 Download PDF

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Publication number
WO2021149410A1
WO2021149410A1 PCT/JP2020/046911 JP2020046911W WO2021149410A1 WO 2021149410 A1 WO2021149410 A1 WO 2021149410A1 JP 2020046911 W JP2020046911 W JP 2020046911W WO 2021149410 A1 WO2021149410 A1 WO 2021149410A1
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Prior art keywords
resin composition
photosensitive resin
positive photosensitive
cured film
group
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PCT/JP2020/046911
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English (en)
French (fr)
Japanese (ja)
Inventor
此島陽平
三井博子
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Toray Industries Inc
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Toray Industries Inc
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Priority to KR1020227015827A priority Critical patent/KR102624811B1/ko
Priority to JP2020570579A priority patent/JP7081696B2/ja
Priority to CN202080093425.5A priority patent/CN114945867B/zh
Publication of WO2021149410A1 publication Critical patent/WO2021149410A1/ja
Anticipated expiration legal-status Critical
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • 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

Definitions

  • the present invention relates to a positive photosensitive resin composition, a cured film, a laminate, a substrate with a conductive pattern, a method for manufacturing a laminate, a touch panel, and an organic EL display device.
  • the touch panel is composed of a display unit such as a liquid crystal panel and a touch panel sensor or the like that detects information input at a specific position.
  • the touch panel method is roughly classified into a resistive film method, a capacitance method, an optical method, an electromagnetic induction method, an ultrasonic method, and the like, depending on the input position detection method.
  • a capacitance type touch panel is widely used because of its optical brightness, excellent design, simple structure, and excellent functionality.
  • the capacitance type touch panel sensor has a second electrode that is orthogonal to the first electrode via an insulating layer, and when a voltage is applied to the electrode on the touch panel surface, the capacitance when a conductor such as a finger touches it.
  • the contact position obtained by detecting the change is output as a signal.
  • the touch panel sensor used in the capacitance method includes, for example, a structure in which electrodes and external connection terminals are formed on a pair of opposing transparent substrates, and electrodes and external connection terminals are formed on both sides of one transparent substrate, respectively.
  • the structure is known.
  • As the wiring electrode used for the touch panel sensor a transparent wiring electrode is generally used from the viewpoint of making the wiring electrode difficult to see, but in recent years, a metal material is used due to higher sensitivity and larger screen. The opaque wiring electrode that was there is widespread.
  • a touch panel sensor having an opaque wiring electrode made of a metal material has a problem that the opaque wiring electrode is visually recognized due to the metallic luster of the opaque wiring electrode.
  • There is a method of forming a light-shielding layer to make it difficult to see. (For example, Patent Document 1)
  • a residue derived from the colorant is likely to be generated on a substrate, particularly on a film containing an organic component, when a pattern is formed, resulting in poor appearance and the like. Transparency was sometimes impaired. Further, when the development time is lengthened in order to suppress the residue, it is difficult to form a fine pattern. Further, when silver electrodes are used as the first electrode and the second electrode, there is also a problem that the components in the light-shielding layer formed on the electrodes diffuse into the insulating layer and become impurities, and silver migration is likely to occur. ..
  • the present invention has low reflectance and can be applied as a light-shielding layer of an opaque wiring electrode, and achieves both fine pattern resolution, ensuring transparency of a base material by suppressing residues on a substrate, and migration resistance. It is an object of the present invention to provide a positive photosensitive resin composition capable of providing a positive photosensitive resin composition.
  • the present inventors have found that the object of the present invention is achieved by combining an alkali-soluble resin having a polymerizable group in the side chain with a photosensitizer and a colorant.
  • the positive photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photosensitive agent (B) and a colorant (C) having a polymerizable group in the side chain, and the polymerizable group is acrylic. It is characterized by being a group and / or a methacrylic group.
  • the positive photosensitive resin composition of the present invention has low reflectance and can be applied as a light-shielding layer for opaque wiring electrodes, ensuring fine pattern resolution and transparency of the substrate by suppressing residues on the substrate. And migration resistance can be compatible.
  • the positive photosensitive resin composition of the present invention contains an alkali-soluble resin (A), a photosensitive agent (B) and a colorant (C) having a polymerizable group in the side chain, and the polymerizable group is an acrylic group and / Or it is a methacrylic group.
  • the positive photosensitive resin composition of the present invention contains an alkali-soluble resin (A) having a polymerizable group in the side chain.
  • an alkali-soluble resin (A) having a polymerizable group in the side chain By containing the alkali-soluble resin (A) having a polymerizable group in the side chain, it is possible to promote dissolution during development, suppress residues, ensure the transparency of the base material, and form a fine pattern. Can be formed. Further, the polymerizable group is crosslinked by the heat treatment after the pattern formation, and the solvent resistance of the obtained cured film is improved.
  • alkali-soluble refers to the property of being soluble in an aqueous alkali solution or an organic alkali.
  • the alkali-soluble resin (A) having a polymerizable group in the side chain 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.
  • the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a thiol group and the like.
  • a carboxyl group is preferable because of its high solubility in an alkaline developer.
  • the polymerizable group is an acrylic group and / or a methacrylic group. Since the polymerizable group is an acrylic group and / or a methacrylic group, the cross-linking reaction by light and / or heat efficiently proceeds and the degree of curing is improved, and as a result, in the light-shielding layer formed on the opaque wiring electrode. It is possible to suppress the diffusion of the component into the insulating layer and improve the migration resistance.
  • alkali-soluble resin examples include, but are not limited to, acrylic polymers, epoxy resins, phenol resins, cardo resins, polysiloxanes, polyimides, polyamides, and polybenzoxazoles. Two or more of these resins may be contained. Among them, acrylic polymers, cardo-based resins, and polysiloxanes are preferable from the viewpoint of ease of introduction of unsaturated double bonds, acrylic polymers and polysiloxanes are more preferable from the viewpoint of weather resistance, and acrylic polymers are preferable from the viewpoint of ease of synthesis. Is even more preferable.
  • the alkali-soluble resin (A) having a polymerizable group in the side chain preferably has an organic group represented by the following general formula (1).
  • an organic group represented by the following general formula (1) in the alkali-soluble resin (A) having a polymerizable group in the side chain the residue is further suppressed during pattern formation to improve the transparency of the base material. It can be secured, and the solvent resistance of the cured film obtained by the subsequent heating step can be further improved.
  • the organic group can be identified by IR analysis, 1 HNMR, GC-MS and MALDI-MS analysis on the alkali-soluble resin (A) having a polymerizable group in the side chain.
  • X represents a hydrocarbon group having 1 to 4 carbon atoms
  • s represents 0 or 1
  • R 1 represents a hydrogen atom or a methyl group.
  • the alkali-soluble resin (A) having a polymerizable group in the side chain has a repeating unit represented by the following general formula (2).
  • R 2 and R 3 represent a hydrogen atom or a methyl group.
  • R 2 and R 3 may be the same or different, respectively.
  • the alkali-soluble resin (A) having a polymerizable group in the side chain preferably has 5 to 50 mol% of the repeating units represented by the general formula (2) in all the repeating units.
  • the repeating unit represented by the general formula (2) is more preferably 10 mol% or more, further preferably 15 mol% or more.
  • the repeating unit represented by the general formula (2) is more preferably 40 mol% or less, and further preferably 35 mol% or less.
  • the alkali-soluble resin (A) having a polymerizable group in the side chain may have a repeating unit other than the repeating unit represented by the general formula (2).
  • a repeating unit other than the repeating unit represented by the general formula (2) a carboxyl group and / or an acid anhydride group-containing (meth) acrylic compound, a (meth) acrylic acid ester, and a (meth) acrylic acid ester are radically copolymerized.
  • the repeating unit contains a compound obtained by an addition reaction of an epoxy compound having an ethylenically unsaturated double bond group.
  • the acrylic polymer is obtained by radical polymerization of a monomer having an ethylenically unsaturated double bond.
  • the repeating unit represented by the general formula (2) is obtained by subjecting an acrylic polymer containing the repeating unit represented by the general formula (3) to an addition reaction of glycidyl (meth) acrylate.
  • the catalyst for radical copolymerization is not particularly limited, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used.
  • the catalyst used for the addition reaction of glycidyl (meth) acrylate is not particularly limited, and known catalysts can be used.
  • dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol dimethyl.
  • Amino catalysts such as benzylamine, tin catalysts such as tin 2-ethylhexanoate (II) and dibutyltin laurate, titanium catalysts such as titanium 2-ethylhexanoate (IV), and phosphorus catalysts such as triphenylphosphine.
  • a catalyst and a chromium-based catalyst such as acetylacetonate chromium and chromium chloride are used.
  • R 4 represents a hydrogen atom or a methyl group.
  • the catalyst used for radical copolymerization of a repeating unit other than the repeating unit represented by the general formula (2) and the catalyst using an epoxy compound having an ethylenically unsaturated double bond group for the addition reaction are also described above. The same is true.
  • Examples of the (meth) acrylic compound containing a carboxyl group and / or an acid anhydride group include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, monosuccinate (2-acryloyloxyethyl), and monophthalate (meth).
  • 2-Acryloyloxyethyl mono (2-acryloyloxyethyl), 2-vinylacetic acid, 2-vinylcyclohexanecarboxylic acid, 3-vinylcyclohexanecarboxylic acid, 4-vinylcyclohexanecarboxylic acid, 2-vinylbenzoic acid , 3-Vinyl benzoic acid, 4-Vinyl benzoic acid, 4-Hydroxyphenyl (meth) acrylate, 2-Hydroxyphenyl (meth) acrylate, (meth) acrylic acid anhydride, itaconic acid, itaconic acid anhydride, amber Examples thereof include acid mono (2-acryloyloxyethyl), phthalate mono (2-acryloyloxyethyl) or tetrahydrophthalate mono (2-acryloyloxyethyl).
  • (meth) acrylic acid ester for example, methyl (meth) acrylate, tricyclodecanyl (meth) acrylate, benzyl (meth) acrylate and the like are used. Further, styrene may be copolymerized with the above-mentioned (meth) acrylic acid or (meth) acrylic acid ester.
  • Examples of the epoxy compound having an ethylenically unsaturated double bond group include glycidyl (meth) acrylate.
  • acrylic polymer a polyfunctional (meth) acrylate compound and a polyvalent mercapto compound polymerized by Michael addition ( ⁇ -position with respect to the carbonyl group) can also be used.
  • the weight average molecular weight (Mw) of the alkali-soluble resin (A) having a polymerizable group in the side chain shall be 1,000 or more and 15,000 or less in terms of polystyrene measured by gel permeation chromatography (GPC). Is preferable.
  • GPC gel permeation chromatography
  • the weight average molecular weight (Mw) is more preferably 5,000 or more, still more preferably 7,000 or more.
  • the weight average molecular weight (Mw) is 15,000 or less, a finer pattern can be formed. In addition, dissolution at the time of development can be further promoted, residue can be further suppressed, and transparency of the base material can be ensured.
  • the weight average molecular weight (Mw) is more preferably 12,000 or less.
  • the content of the alkali-soluble resin (A) having a polymerizable group in the side chain is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application.
  • the solid content is 100% by mass, it is generally 10% by mass or more and 70% by mass or less.
  • the positive photosensitive resin composition of the present invention contains a photosensitive agent (B).
  • the photosensitizer (B) has a property of increasing the alkali solubility of the light-irradiated portion of the alkali-soluble resin (A) having a polymerizable group in the side chain by generating an acid when irradiated with light.
  • Alkali-soluble contrast can be obtained, fine patterns can be formed, and residues can be suppressed to ensure the transparency of the base material.
  • the photosensitizer include a quinone diazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt. Of these, a quinonediazide compound is preferable because a finer pattern can be obtained.
  • the quinone diazide preferably contains a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group.
  • the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinone diazidosulfonyl ester compound has absorption in the g-line region of a mercury lamp and is suitable for g-line exposure.
  • the content of the photosensitive agent (B) is not particularly limited, but is preferably 0.01 to 50% by mass with respect to 100% by mass of the solid content.
  • the content of the photosensitizer (B) is 0.01% by mass or more, a finer pattern can be formed. Further, since the alkali solubility of the exposed portion is promoted, the residue can be further suppressed and the transparency of the base material can be ensured.
  • the content of the photosensitizer (B) is more preferably 10% by mass or more. Further, when the content of the photosensitizer (B) is 50% by mass or less, light can be transmitted to the bottom of the film, and a pattern can be obtained with high exposure sensitivity.
  • the content of the photosensitizer (B) is more preferably 40% by mass or less.
  • the above polyhydroxy compound or polyamino compound may be used as it is without being esterified with quinonediazide sulfonic acid.
  • the amount of the hydroxy compound or polyamino compound added is preferably 1 to 50% by mass with respect to 100% by mass of the solid content.
  • the positive resin composition obtained by adding 1% by mass or more of an unesterified hydroxy compound or polyamino compound hardly dissolves in an alkaline developer before exposure, and easily becomes an alkaline developer when exposed. Since it dissolves, there is little film loss due to development, and development becomes easy in a short time.
  • the amount of the hydroxy compound or polyamino compound added is more preferably 3% by mass or more.
  • the solubility in the alkaline developer can be further improved, and a finer pattern can be formed.
  • the amount of the hydroxy compound or polyamino compound added is more preferably 40% by mass or less.
  • the positive photosensitive resin composition of the present invention contains a colorant (C).
  • the colorant (C) refers to a compound that colors by absorbing light in the entire range or a part of the wavelength of visible light (380 to 780 nm).
  • the positive photosensitive resin composition of the present invention when the positive photosensitive resin composition of the present invention is formed on the conductive layer, the light reflected by the conductive layer is shielded, so that the conductive layer becomes difficult to see. ..
  • Examples of the colorant (C) include compounds that absorb light having a wavelength of visible light and color black, red, orange, yellow, green, blue, or purple. By combining these colorants alone or in combination of two or more colors, the light reflected by the conductive layer can be shielded.
  • the colorant (C) preferably has an aromatic group.
  • an aromatic group By having an aromatic group, it interacts with the polymerizable group of the alkali-soluble resin (A) having a polymerizable group in the side chain, increases the solubility in an alkaline developer, and further suppresses the residue of the base material. Transparency can be ensured.
  • Examples of the colorant (C) include a black agent (Ca) and / or a colorant other than black (Cb).
  • the blackening agent (Ca) is a compound that is colored black by absorbing light in the entire wavelength range of visible light. By containing the blackening agent (Ca), the light blocking property can be improved by blocking the light reflected by the conductive layer.
  • the colorant (Cb) other than black refers to a compound that colors red, orange, yellow, green, blue, or purple by absorbing light having a partial wavelength of visible light. By combining two or more colors of these colorants (Cb), it is possible to color the color in a pseudo-black color, and it is possible to improve the light-shielding property. From the viewpoint of light-shielding property, it is preferable to use a blackening agent (Ca) because it has excellent hiding power.
  • the colorant (C) preferably contains one or more selected from organic pigments (C1), inorganic pigments (C2) and dyes (C3), which will be described later.
  • organic pigments (C1) is preferable, and the black organic pigment is more preferable, from the viewpoint of heat resistance and light-shielding property.
  • the colorant (C) contains an organic pigment (C1).
  • the organic pigment (C1) it is possible to impart a light-shielding property to the cured film of the positive photosensitive resin composition, and it has a high hiding property and is less likely to fade due to ultraviolet rays or the like.
  • the black agent (Ca) and / or the colorant (Cb) other than black may be the organic pigment (C1).
  • the number average particle size of the organic pigment (C1) is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and even more preferably 10 to 200 nm. When the number average particle size of the organic pigment (C1) is within the above range, the light-shielding property of the cured film of the positive photosensitive resin composition and the dispersion stability of the organic pigment (C1) can be improved.
  • the number average particle size of the organic pigment (C1) is determined by a submicron particle size distribution measuring device (N4-PLUS; manufactured by Beckman Coulter Co., Ltd.) or a zeta potential / particle size / molecular weight measuring device (Zetasizer Nano ZS). It can be obtained by measuring the laser scattering of the organic pigment (C1) in the solution due to Brownian motion (dynamic light scattering method) using Sysmex Co., Ltd. Further, the number average particle size of the organic pigment (C1) in the cured film obtained from the resin composition can be determined by measuring using SEM and TEM. The number average particle size of the organic pigment (C1) is directly measured with a magnification of 50,000 to 200,000 times.
  • the number average particle size can be calculated by the average value of the particle sizes of 100 randomly selected primary particles.
  • the organic pigment (C1) is a true sphere
  • the diameter of the true sphere is measured and used as the number average particle size.
  • the organic pigment (C1) is not a true sphere
  • the longest diameter (hereinafter, "major axis diameter”) and the longest diameter in the direction orthogonal to the major axis diameter (hereinafter, “minor axis diameter”) are measured, and the major axis is measured.
  • the biaxial average diameter which is the average of the diameter and the minor axis diameter, is defined as the number average particle diameter.
  • organic pigment (C1) examples include phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, pyranthron pigments, dioxazine pigments, thioindigo pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, slene pigments, and indolin.
  • anthraquinone pigments from the viewpoint of heat resistance, anthraquinone pigments, quinacridone pigments, pyranthron pigments, diketopyrrolopyrrole pigments, benzofuranone pigments, perylene pigments, condensed azo pigments and carbon black are preferable.
  • carbon black is more preferable from the viewpoint of dispersion stability and ensuring transparency of the base material by suppressing residues by having an aromatic group.
  • phthalocyanine pigment examples include a copper phthalocyanine compound, a halogenated copper phthalocyanine compound, and a metal-free phthalocyanine compound.
  • anthraquinone-based pigment examples include aminoanthraquinone-based compounds, diaminoanthraquinone-based compounds, anthrapyrimidine-based compounds, flavantron-based compounds, antoanthron-based compounds, indantron-based compounds, pyranthron-based compounds, and biolantron-based compounds.
  • Examples of the azo pigment include a disazo compound or a polyazo compound.
  • Examples of carbon black include channel black, furnace black, thermal black, acetylene black and lamp black.
  • the content ratio of the organic pigment (C1) is preferably 5 to 50% by mass with respect to 100% by mass of the solid content.
  • the content ratio of the organic pigment (C1) is 5% by mass or more, the light-shielding property can be further improved.
  • the content ratio of the organic pigment (C1) is more preferably 10% by mass or more.
  • the content ratio of the organic pigment (C1) is 50% by mass or less, the development residue can be further reduced and the transparency of the base material can be ensured.
  • the content ratio of the organic pigment (C1) is more preferably 40% by mass or less than the beam.
  • the colorant (C) contains an inorganic pigment (C2).
  • the inorganic pigment (C2) it is possible to impart light-shielding properties to the film of the positive photosensitive resin composition, and since it is an inorganic substance and is superior in heat resistance and weather resistance, the film of the resin composition Heat resistance and weather resistance can be improved.
  • the black agent (Ca) and / or the colorant (Cb) other than black may be the inorganic pigment (C2).
  • Examples of the inorganic pigment (C2) include metals such as titanium, barium, zirconium, lead, silicon, aluminum, magnesium, molybdenum, cadonium, tin, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium or silver. Fine particles, oxides of the above metal elements, composite oxides, sulfides, sulfates, nitrates, carbonates, nitrides, carbides or oxynitrides. Of these, metal nitride particles are preferable from the viewpoint of further improving pattern processability and light-shielding property.
  • fine particles of titanium, zirconium or silver, oxides, composite oxides, sulfides, nitrides, carbides or oxynitrides are preferable, and zirconium nitride particles are particularly preferable.
  • the content ratio of the inorganic pigment (C2) is preferably 5 to 50% by mass with respect to 100% by mass of the solid content.
  • the content ratio of the inorganic pigment (C2) is more preferably 10% by mass or more.
  • the content ratio of the inorganic pigment (C2) is 50% by mass or less, the development residue can be further reduced and the transparency of the base material can be ensured.
  • the content ratio of the inorganic pigment (C2) is more preferably 40% by mass or less.
  • the colorant (C) contains a dye (C3).
  • the black agent (Ca) and / or the colorant (Cb) other than black may be the dye (C3).
  • Dye (C3) is a compound that colors an object by chemically adsorbing or strongly interacting with a substituent such as an ionic group or a hydroxy group in the dye (C3) on the surface structure of the object. Generally, it is soluble in a solvent or the like. Further, in the coloring with the dye (C3), since each molecule is adsorbed on the object, the coloring power is high and the coloring efficiency is high.
  • Examples of the dye (C3) include anthraquinone dyes, azo dyes, azine dyes, phthalocyanine dyes, methine dyes, oxazine dyes, quinoline dyes, indigo dyes, indigoid dyes, carbonium dyes, and slene.
  • Examples thereof include based dyes, perinone dyes, perylene dyes, triarylmethane dyes and xanthene dyes. From the viewpoint of solubility in a solvent and heat resistance, anthraquinone dyes, azo dyes, azine dyes, methine dyes, triarylmethane dyes, and xanthene dyes are preferable.
  • Examples of the dye that colors black include solvent black 3, 5, 7, 22, 27, 29 or 34, modern black 1, 11 or 17, acid black 2 or 52, or direct black 19 or 154. (All numerical values are CI numbers).
  • "NUBIAN” registered trademark
  • Examples of the dye that colors red include Direct Red 9, 28, 81, or 83 (all numerical values are CI numbers).
  • Examples of the dye that colors orange include Basic Orange 21 or 23 (all numerical values are CI numbers).
  • Examples of the dye that colors yellow include Direct Yellow 8, 9, 11, 27 or 44, or Basic Yellow 1, 28 or 40 (all numerical values are CI numbers).
  • Examples of the dye that colors green include acid green 16 (all numerical values are CI numbers).
  • Examples of the dye that colors blue include acid blue 9, 45, 80, 83, 90 or 185 (all numerical values are CI numbers).
  • Examples of the dye that colors purple include Direct Violet 51 or 66, or Basic Violet 1, 2, or 3 (all numerical values are CI numbers).
  • the content ratio of the dye (C3) is preferably 0.01 to 50% by mass with respect to 100% by mass of the solid content.
  • the content ratio of the dye (C3) is 0.01% by mass or more, the light-shielding property can be further improved.
  • the content ratio of the dye (C3) is more preferably 0.05% by mass or more.
  • the content ratio of the dye (C3) is 50% by mass or less, the development residue can be further reduced and the transparency of the base material can be ensured.
  • the content ratio of the dye (C3) is more preferably 40% by mass or less than the beam.
  • the positive photosensitive resin composition of the present invention preferably further contains a dispersant.
  • the dispersant refers to a compound having a surface affinity group that interacts with the surface such as the above-mentioned colorant (C) and a dispersion stabilizing structure that improves the dispersion stability of the colorant (C).
  • the dispersion-stabilizing structure of the dispersant include a polymer chain and / or a substituent having an electrostatic charge.
  • Examples of the dispersant having a surface affinity group include a dispersant having an amine value and / or an acid value, and a dispersant having neither an amine value nor an acid value. From the viewpoint of improving the dispersion stability of the colorant (C), a dispersant having only an amine value and a dispersant having an amine value and an acid value are preferable.
  • the amino group and / or the acidic group, which are the surface affinity groups have a structure in which a salt is formed with an acid and / or a base.
  • Examples of the dispersant having only an amine value include "DISPERBYK” (registered trademark) -161, -167, -2000, -2008, -2009, -2022, -2050, and -2055. -2150, -2155, -2163, -2164, or -2061, "BYK” (registered trademark) -9075, -9077, -LP-N6919, -LP-N21116 or -LP -N21324 (all of which are manufactured by Big Chemie Japan Co., Ltd.) can be mentioned.
  • Dispersants having an amine value and an acid value include, for example, "DISPERBYK” (registered trademark) -2001, -2013, -2020, -2025, -187 or -191, "BYK” (registered trademark). ) -9076 (Made by Big Chemie Japan Co., Ltd.).
  • Dispersants having only an acid value include, for example, "DISPERBYK” (registered trademark) -102, -110, -111, -118, -170, -171, -174, -2060 or The same -2096 can be mentioned.
  • Examples of the dispersant having neither an amine value nor an acid value include "DISPERBYK” (registered trademark) -103, -2152, -2200 or -192 (all of which are manufactured by Big Chemie Japan Co., Ltd.). ).
  • the amine value of the dispersant is preferably 1 mgKOH / g or more. When the amine value is within the above range, the dispersion stability of the colorant (C) can be further improved. On the other hand, the amine value is preferably 150 mgKOH / g or less. When the amine value is within the above range, the storage stability of the resin composition can be improved.
  • the amine value here refers to the weight of the acid equivalent to potassium hydroxide that reacts with 1 g of the dispersant, and the unit is mgKOH / g. It can be obtained by neutralizing 1 g of the dispersant with an acid and then titrating with an aqueous solution of potassium hydroxide. From the value of the amine value, the amine equivalent (unit: g / mol), which is the weight of the resin per 1 mol of amino groups, can be calculated, and the number of amino groups in the dispersant can be determined.
  • the acid value of the dispersant is preferably 1 mgKOH / g or more. When the acid value is within the above range, the dispersion stability of the colorant (C) can be further improved. On the other hand, the acid value is preferably 200 mgKOH / g or less. When the acid value is within the above range, the storage stability of the resin composition can be improved.
  • the acid value here means the weight of potassium hydroxide that reacts with 1 g of the dispersant, and the unit is mgKOH / g. It can be obtained by titrating 1 g of the dispersant with an aqueous solution of potassium hydroxide. From the value of the acid value, the acid equivalent (unit: g / mol), which is the weight of the resin per 1 mol of the acidic group, can be calculated, and the number of acidic groups in the dispersant can be obtained.
  • Dispersants whose dispersion-stabilized structure is a substituent having a polymer chain include acrylic resin-based dispersants, polyoxyalkylene ether-based dispersants, polyester-based dispersants, polyurethane-based dispersants, polyol-based dispersants, and polyethyleneimine-based dispersants. Dispersants or polyallylamine-based dispersants can be mentioned. From the viewpoint of pattern processability with an alkaline developer, an acrylic resin-based dispersant, a polyoxyalkylene ether-based dispersant, a polyester-based dispersant, a polyurethane-based dispersant, or a polyol-based dispersant is preferable.
  • the content ratio of the dispersant in the positive photosensitive resin composition of the present invention is preferably 1 to 60% by mass when the colorant (C) is 100% by mass.
  • the content ratio of the dispersant is more preferably 5% by mass or more.
  • the content ratio of the dispersant is 60% by mass or less, the heat resistance of the cured film can be improved.
  • the content ratio of the dispersant is more preferably 50% by mass or less.
  • the resin composition of the present invention may further contain a thermal cross-linking agent.
  • the thermal cross-linking agent refers to a compound having at least two thermally reactive functional groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, and an oxetanyl group.
  • HMOM-TPPHBA HMOMTPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), "NIKALAC” (registered trademark) MX-290, " NIKALAC "MX-280,” NIKALAC “MX-270,” NIKALAC “MX-279,” NIKALAC “MW-100LM,” NIKALAC “MX-750LM (trade name, manufactured by Sanwa Chemical Co., Ltd.), DCL- 2001 (trade name, manufactured by Daito Chemix Co., Ltd.) can be mentioned.
  • Preferred examples of compounds having at least two epoxy groups are “Epolite” (registered trademark) 40E, "Epolite” 100E, “Epolite” 200E, “Epolite” 400E, "Epolite” 70P, “Epolite” 200P, “Epolite”.
  • Preferred examples of the compound having at least two oxetanyl groups include, for example, Ethanacole EHO, Ethanacole OXBP, Ethanacole OXTP, Ethanacole OXMA (all manufactured by Ube Industries, Ltd.), oxetaneated phenol novolac, and the like.
  • the thermal cross-linking agent may be contained in combination of two or more types.
  • NIKALAC MX-290 "NIKALAC” MX-280, “NIKALAC” MX-270, “NIKALAC” MX-279, from the viewpoint of heat resistance of the cured film obtained after curing by heat. It is preferably a compound selected from any of "NIKALAC” MW-100LM, “NIKALAC” MX-750LM, and DCL-2001.
  • the content of the thermal cross-linking agent is preferably 0.1 to 50% by mass with respect to 100% by mass of the solid content.
  • the content of the thermal cross-linking agent is more preferably 1% by mass or more.
  • the content of the thermal cross-linking agent is 50% by mass or less, the amount of outgas from the cured film can be reduced.
  • the content of the thermal cross-linking agent is more preferably 30% by mass or less.
  • the positive photosensitive resin composition of the present invention preferably further contains a silane coupling agent.
  • the silane coupling agent refers to a compound having a hydrolyzable silyl group or silanol group.
  • silane coupling agent trifunctional organosilane or tetrafunctional organosilane is preferable.
  • trifunctional organosilane examples include vinyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2- (3,4-epoxy).
  • tetrafunctional organosilane examples include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, and tetraacetoxysilane.
  • silane coupling agent vinyl trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-glycid from the viewpoint of improving the adhesion to the underlying conductive layer or insulating layer.
  • the content of the silane coupling agent is preferably 0.1 to 15% by mass with respect to 100% by mass of the solid content.
  • the content of the silane coupling agent is more preferably 0.5% by mass or more.
  • the resolution after development can be further improved.
  • the content of the silane coupling agent is more preferably 10% by mass or less.
  • the positive photosensitive resin composition of the present invention may contain various surfactants such as various fluorine-based surfactants and silicone-based surfactants in order to improve the flowability at the time of coating.
  • the type of surfactant is not particularly limited, and for example, fluorine-based surfactants such as "Megafuck” (registered trademark) "F477 (trade name)” (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), " BYK-333 (trade name) ”, (manufactured by Big Chemie Japan Co., Ltd.) and other silicone-based surfactants, polyalkylene oxide-based surfactants, poly (meth) acrylate-based surfactants and the like can be used. Two or more of these may be used.
  • the positive photosensitive resin composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber By containing the ultraviolet absorber, the light resistance of the obtained cured film is improved, and the resolution after development is further improved.
  • the ultraviolet absorber is not particularly limited and known ones can be used, but benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds are preferable from the viewpoint of transparency and non-coloring property.
  • the photosensitive resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing an appropriate amount of the polymerization inhibitor, the resolution after development is further improved.
  • the polymerization inhibitor is not particularly limited and known ones can be used. Examples thereof include di-t-butylhydroxytoluene, hydroquinone, p-methoxyphenol, 1,4-benzoquinone and t-butylcatechol.
  • Examples of commercially available polymerization inhibitors include "IRGANOX 1010", “IRGANOX 245", "IRGANOX 3114", and "IRGANOX 565" (all manufactured by BASF).
  • the photosensitive resin composition of the present invention may contain a solvent.
  • the solvent contained in the photosensitive resin composition of the present invention preferably has a boiling point of 110 to 250 ° C. under atmospheric pressure, and more preferably 200 ° C. or lower. In addition, you may use a plurality of kinds of these solvents. If the boiling point is higher than 200 ° C., the amount of residual solvent in the film increases, the film shrinkage during curing becomes large, and good flatness cannot be obtained. On the other hand, if the boiling point is lower than 110 ° C., the coating film is dried too quickly and the film surface is roughened, resulting in poor coating film properties. Therefore, it is preferable that the solvent having a boiling point of 200 ° C. or lower under atmospheric pressure is 50% by mass or more of the total amount of the solvent in the photosensitive resin composition.
  • the solvent include, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, ethylene glycol monomethyl ether acetate, 1-methoxypropyl-2-acetate, and dipropylene glycol.
  • examples thereof include methyl ether and diacetone alcohol.
  • the content of the solvent is not particularly limited, and any amount can be used depending on the coating method and the like.
  • the film is formed by spin coating, it is generally 50% by mass or more and 95% by mass or less of the entire photosensitive resin composition.
  • the positive photosensitive resin composition of the present invention may contain additives such as a dissolution inhibitor, a stabilizer, and an antifoaming agent, if necessary.
  • the solid content concentration of the positive photosensitive resin composition of the present invention is not particularly limited, and an arbitrary amount of solvent or solute can be used depending on the coating method and the like.
  • the solid content concentration is generally 5% by mass or more and 50% by mass or less.
  • the solid content is a photosensitive resin composition obtained by removing the solvent.
  • a typical method for producing the positive photosensitive resin composition of the present invention will be described.
  • an alkali-soluble resin (A) having a polymerizable group in the side chain, a photosensitizer (B), a colorant (C) and, if necessary, other additives are added to an arbitrary solvent, stirred and dissolved, and then dissolved.
  • the obtained solution is filtered to obtain a positive photosensitive resin composition.
  • a disperser such as a ball mill, sand grinder, 3-roll mill, mild disperser, medialess disperser, etc., and use the dispersant and the colorant (C) in advance in an organic solvent.
  • the cured film of the present invention is obtained by curing the positive photosensitive resin composition.
  • the positive photosensitive resin composition can be cured by a method described later.
  • the film thickness of the cured film of the present invention is not particularly limited, but is preferably 0.1 to 10 ⁇ m. When the film thickness of the cured film is 0.1 ⁇ m or more, the light-shielding property can be further improved.
  • the film thickness of the cured film is more preferably 0.3 ⁇ m or more. On the other hand, when the film thickness of the cured film is 10 ⁇ m or less, light reaches a deep part at the time of exposure, and a finer pattern can be formed.
  • the film thickness of the cured film is more preferably 7 ⁇ m or less, still more preferably 5 ⁇ m or less.
  • the reflectance of the cured film of the present invention at a wavelength of 550 nm is preferably 0.01 to 20%. By setting the reflectance to 0.01% or more, the conductive layer can be made difficult to see. On the other hand, when the reflectance is 20% or less, the light reaches a deep part at the time of exposure, and a finer pattern can be formed. The reflectance is more preferably 15% or less, still more preferably 10% or less. The reflectance refers to the reflectance at a film thickness of 1.0 ⁇ m. The reflectance can be adjusted by selecting the exposure amount, the developing time, and the thermosetting temperature. The reflectance of the cured film of the present invention can be measured with a reflectance meter for a cured film having a size of 0.1 mm square or more on a transparent substrate.
  • the cured film of the present invention can be used as a light-shielding layer for an opaque wiring electrode for a touch panel, a light-shielding film such as a black matrix for a color filter or a black column spacer for a liquid crystal display, a pixel division layer for an organic EL display device, or a TFT flattening layer. It can be preferably used. Among these, since it is possible to form a fine pattern and has a low reflectance, it can be particularly preferably used as a light-shielding layer of an opaque electrode for a touch panel, a pixel dividing layer of an organic EL display device, or a TFT flattening layer.
  • the positive photosensitive resin composition of the present invention is applied onto a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating and the like.
  • Prebak the above coating film with a heating device such as a hot plate or oven is preferably carried out in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after prebaking is preferably 0.1 to 15 ⁇ m.
  • the coating film is exposed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
  • the exposure intensity is about 10 to 4000 J / m2 (wavelength 365 nm exposure amount conversion), and this light is irradiated with or without a desired mask.
  • the exposure light source is not limited, and ultraviolet rays such as g-line, h-line, and i-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, and the like can be used.
  • the developing solution includes inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), triethanolamine, diethanolamine, and monoethanol.
  • inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate or potassium carbonate, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH), triethanolamine, diethanolamine, and monoethanol.
  • organic alkalis such as alcohol amines such as amines, dimethylaminoethanol and diethylaminoethanol.
  • a water-soluble organic solvent such as ethanol, ⁇ -butyrolactone, dimethylformamide or N-methyl-2-pyrrolidone may be appropriately added to these alkaline developers.
  • a surfactant such as a nonionic surfactant to these alkaline developers.
  • the coating film After development, it is preferable to rinse the coating film with water, and then the coating film can be dried and baked in the range of 50 to 130 ° C.
  • the method for producing a cured film of the present invention preferably includes a step of heating the coating film at 150 to 250 ° C.
  • the laminate of the present invention has a conductive layer and a cured film of the present invention.
  • the cured film of the present invention can form a fine pattern while ensuring low reflectance and transparency of the base material without residue, for example, a light-shielding layer of an opaque wiring electrode which is a conductive layer of a touch panel. Can be suitably used as.
  • the ratio of the film thickness of the cured film to the film thickness of the conductive layer is preferably 1/2 to 5.
  • the film thickness ratio is preferably 1/2 to 5.
  • the laminate of the present invention preferably has an insulating layer in addition to the conductive layer and the cured film of the present invention.
  • an insulating layer By having the insulating layer, defects such as short circuits occurring between the conductive layers can be suppressed, and a highly reliable laminated body can be formed. Further, by protecting the light-shielding layer, it is possible to suppress scratches and prevent poor visibility.
  • the insulating material contained in the above-mentioned insulating layer is not particularly limited, and examples thereof include acrylic polymers, epoxy resins, phenol resins, cardo resins, polysiloxanes, polyimides, polyamides, and polybenzoxazoles. Two or more of these may be contained.
  • Examples of the conductive material contained in the above-mentioned conductive layer include copper, silver, gold, aluminum, chromium, molybdenum, and titanium. In addition to the above, it may be combined with a conductive material forming a transparent electrode, for example, ITO, IZO (indium zinc oxide), AZO (aluminum-added zinc oxide), ZnO 2, or the like. Among these, silver having the lowest specific resistance value is preferable. When the specific resistance value is low, a highly sensitive touch panel can be manufactured. Further, since a finer wiring pattern can be formed, it is preferable that the average primary particle size of silver is 10 to 200 nm.
  • the average primary particle size of silver can be calculated from the average value of the particle sizes of 100 primary particles randomly selected using a scanning electron microscope.
  • the particle size of each primary particle can be calculated from the average value obtained by measuring the major axis and the minor axis of the primary particle.
  • the conductive layer contains 5 to 35% by mass of an organic component having an alkali-soluble group.
  • the content ratio of the organic component having an alkali-soluble group is 5% by mass or more, the photosensitive characteristics can be improved and a finer pattern can be formed.
  • the specific resistance value can be reduced and a highly sensitive touch panel can be formed.
  • the alkali-soluble group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, and a thiol group.
  • the organic component having an alkali-soluble group the organic component described in the positive photosensitive resin composition can be used.
  • FIG. 1 is a schematic view of a laminated body having an opaque wiring electrode 2 on a transparent substrate 1 and a light-shielding layer 3 made of the cured film of the present invention on the opaque wiring electrode 2.
  • the laminate shown in FIG. 1 can be obtained through a step of exposing from the opposite surface side of the opaque wiring electrode forming surface of the transparent substrate in the method for manufacturing the laminate described later.
  • FIG. 2 has an opaque wiring electrode 2 (first opaque wiring electrode) and an insulating layer 4 on a transparent substrate 1, and an opaque wiring electrode 2 (second opaque wiring electrode) on the insulating layer 4. Further, it is a schematic view of a laminated body having a light-shielding layer 3 made of the cured film of the present invention at a portion corresponding to the opaque wiring electrode 2 (the first opaque wiring electrode and the second opaque wiring electrode).
  • the first opaque wiring electrode, the insulating layer, and the second opaque wiring electrode are formed on one side of the transparent substrate in the method for manufacturing the laminate described later, and the positive photosensitive resin of the present invention is formed. It can be obtained through a step of applying the composition and exposing it from the opposite surface side of the opaque wiring electrode forming surface of the transparent substrate.
  • the method for producing a laminate of the present invention includes a step of forming an opaque wiring electrode on one surface of a transparent substrate and a step of applying the positive photosensitive resin composition of the present invention to the opaque wiring electrode forming surface of the transparent substrate.
  • FIG. 3 shows a schematic view of an example of the method for producing a laminated body of the present invention.
  • the opaque wiring electrode 2 is formed on one side of the transparent substrate 1.
  • the step of forming the opaque wiring electrode on one side of the transparent substrate is the step of forming the first opaque wiring electrode on one side of the transparent substrate, the step of forming the insulating layer on the first opaque wiring electrode, and the insulation. It may have a step of forming a second opaque wiring electrode on the layer.
  • Examples of the method for forming the opaque wiring electrode include a method of forming a pattern by a photolithography method using a photosensitive conductive composition, and a pattern by screen printing, gravure printing, inkjet, etc. using a conductive composition (conductive paste). Examples thereof include a method of forming, a method of forming a film of a metal, a metal composite, a composite of a metal and a metal compound, a metal alloy, and the like, and forming the film by a photolithography method using a resist. Among these, since fine wiring can be formed, a method of forming by a photolithography method using a photosensitive conductive composition is preferable. When two or more opaque wiring electrodes are formed via the insulating layer, each opaque wiring electrode may be formed by the same method, or different methods may be combined. An insulating layer may be formed on the opaque wiring electrode of the obtained laminate with the opaque wiring electrode.
  • Examples of the method for forming the insulating layer include a method of forming a pattern by a photolithography method using a photosensitive insulating composition, a method of applying the insulating composition and drying it, and an adhesive on the opaque wiring electrode forming surface side.
  • a method of sticking a transparent substrate through the above can be mentioned.
  • a method of forming by a photolithography method using a photosensitive insulating composition is preferable.
  • the adhesive may be formed on the base material with the opaque wiring electrode and the transparent substrate may be attached, or the transparent substrate with the adhesive may be attached. May be good.
  • the positive photosensitive resin composition 5 of the present invention is applied to the opaque wiring electrode forming surface of the transparent substrate 1.
  • the laminate of the present invention When the laminate of the present invention is used as a touch panel sensor, it is not necessary to apply the positive photosensitive resin composition of the present invention to the connection portion with the flexographic substrate, if necessary.
  • the positive photosensitive resin composition 5 of the present invention is exposed from the opposite side of the opaque wiring electrode forming surface of the transparent substrate and developed to obtain an opaque wiring electrode.
  • a light-shielding layer is formed on the corresponding portion.
  • the step of forming the opaque wiring electrode on one side of the transparent substrate is the step of forming the first opaque wiring electrode on one side of the transparent substrate, the step of forming the insulating layer on the first opaque wiring electrode, and the step of forming the insulating layer.
  • the step of forming the second opaque wiring electrode on the insulating layer it is preferable to form a light-shielding layer at a portion corresponding to the first opaque wiring electrode and the second opaque wiring electrode.
  • the substrate with a conductive pattern of the present invention is a substrate with a conductive pattern having a substrate, a conductive pattern formed on the substrate, and a cured film of the present invention, and has the cured film on at least a part of the conductive pattern forming region. However, it does not have the cured film on the non-conducting pattern region. With such a configuration, it is possible to suppress the reflection of the conductive pattern while ensuring the transparency of the base material.
  • the substrate with a conductive pattern includes a connecting portion
  • Synthesis Example 2 Acrylic polymer (a1-2) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 3 Acrylic polymer (a1-3) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 4 Acrylic polymer (a1-4) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 5 Acrylic polymer (a1-5) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 6 Acrylic polymer (a1-6) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 51.7 g of methacrylic acid, 52.9 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, and the mixture was stirred at room temperature for a while, and the flask was stirred. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 7 Acrylic polymer (a1-7) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 8 Acrylic polymer (a1-8) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 60.3 g of methacrylic acid, 35.2 g of benzyl methacrylate, and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 9 Acrylic polymer (a1-9) 0.5 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 2 hours.
  • Synthesis Example 10 Acrylic polymer (a1-10) 0.5 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 4 hours.
  • Synthesis Example 11 Acrylic polymer (a1-11) 1.5 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 12 Acrylic polymer (a1-12) 2.0 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 13 Acrylic polymer (a1-13) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 14 Acrylic polymer (a1-14) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • Synthesis Example 15 Acrylic polymer (a1'-1) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours.
  • allylglycidyl ether 1 g of dimethylbenzylamine, 0.2 g of p-methoxyphenol and 100 g of PGMEA were added to the obtained solution, and the mixture was heated and stirred at 90 ° C. for 4 hours to obtain the acrylic.
  • PGMEA was added to the polymer solution so that the solid content concentration became 40 wt% to obtain a solution of acrylic polymer (a1'-1).
  • the polystyrene-equivalent weight average molecular weight Mw measured by the GPC method was 10,000.
  • Synthesis Example 16 Acrylic polymer (a1'-2) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. After that, 34.4 g of methacrylic acid, 61.7 g of benzyl methacrylate, 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate, and 21.3 g of glycidyl methacrylate were charged. , Stir for a while at room temperature, sufficiently replace the inside of the flask with nitrogen by bubbling, heat and stir at 70 ° C. for 5 hours, add PGMEA to the obtained acrylic polymer solution so that the solid content concentration becomes 40 wt%, and add acrylic acid. A solution of the polymer (a1'-2) was obtained. The polystyrene-equivalent weight average molecular weight Mw measured by the GPC method was 12,000.
  • Synthesis Example 17 Acrylic polymer (a1'-3) 1 g of AIBN and 50 g of PGMEA were placed in a 500 ml flask. Then, 43.0 g of methacrylic acid, 70.5 g of benzyl methacrylate and 22.0 g of tricyclo [5.2.1.0 (2,6)] decane-8-yl methacrylate were charged, stirred at room temperature for a while, and flasked. After sufficiently replacing the inside with nitrogen by bubbling, the mixture was heated and stirred at 70 ° C. for 5 hours. Next, PGMEA was added to the obtained acrylic polymer solution so that the solid content concentration was 40 wt% to obtain a solution of the acrylic polymer (a1'-3). The polystyrene-equivalent weight average molecular weight Mw measured by the GPC method was 11,000.
  • conductive fine particles manufactured by Nisshin Engineering Co., Ltd.
  • a carbon compound 80.0 g
  • BYK-21116 4.06 g
  • PGMEA 196.14 g
  • the mixed solution was further dispersed using a mill-type disperser filled with zirconia beads to obtain a silver fine particle dispersion.
  • Photosensitive insulating material The method for producing the photosensitive insulating material is shown below.
  • ⁇ Silver ink material ( ⁇ ) pattern production> After drying the silver ink material ( ⁇ ) on the substrate or on the substrate with an opaque wiring electrode having an insulating layer using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.), the film thickness becomes 1 ⁇ m. After spin coating at a predetermined rotation speed as described above, a prebaked film was prepared by prebaking at 100 ° C. for 2 minutes using a hot plate (“SCW-636 (trade name)” manufactured by Dainippon Screen Mfg. Co., Ltd.).
  • SCW-636 trade name
  • a parallel light mask aligner (“PLA-501F (trade name)” manufactured by Canon Inc.) was used as a light source, and an exposure amount of 500 mJ / cm 2 (wavelength) was passed through a desired mask. It was exposed at (365 nm conversion) to prepare a mesh-shaped pattern having a pitch of 300 ⁇ m shown in FIG. After that, using an automatic developing device (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), shower development was performed with a 0.07 wt% TMAH aqueous solution for 60 seconds, then rinsed with water for 30 seconds, and pattern processing was performed. Was done.
  • AD-2000 automatic developing device
  • the patterned substrate was post-baked at 230 ° C. for 60 minutes (in the air) using an oven (“IHPS-222 (trade name)” manufactured by ESPEC CORPORATION) to prepare a substrate with an opaque wiring electrode.
  • IHPS-222 trade name
  • ESPEC CORPORATION an oven
  • ⁇ Pattern production of photosensitive insulating material ( ⁇ )> The photosensitive insulating material ( ⁇ ) is spin-coated on the obtained substrate with an opaque wiring electrode using a spin coater at a predetermined rotation speed so that the film thickness becomes 2.5 ⁇ m after drying, and then a hot plate is used. Prebaked at 100 ° C. for 2 minutes to prepare a prebaked film.
  • the prebake film was exposed to an exposure amount of 200 mJ / cm 2 (wavelength 365 nm conversion) through an exposure mask having a desired pattern using an ultrahigh pressure mercury lamp as a light source using a parallel light mask aligner. Then, using an automatic developing apparatus, shower development was performed with 0.07 wt% TMAH aqueous solution for 60 seconds, and then rinse with water for 30 seconds to perform pattern processing.
  • the patterned substrate was post-baked at 230 ° C. for 60 minutes (in air) using an oven to prepare a substrate with an opaque wiring electrode having an insulating layer.
  • ⁇ Preparation of cured film of positive photosensitive resin composition The positive photosensitive resin composition is dried on the opaque wiring electrode forming surface of the obtained substrate with opaque wiring electrodes or the substrate with opaque wiring electrodes having an insulating layer using a spin coater, and the thickness becomes 1.0 ⁇ m. After spin coating at a predetermined number of revolutions as described above, a prebaked film was prepared by prebaking at 100 ° C. for 2 minutes using a hot plate. The prebake film is exposed to an exposure amount of 500 mJ / cm 2 (wavelength 365 nm conversion) from the opposite side of the opaque wiring electrode forming surface using an ultra-high pressure mercury lamp as a light source and an opaque wiring electrode as a mask using a parallel light mask aligner. did. Then, using an automatic developing apparatus, shower development was performed with 0.07 wt% TMAH aqueous solution for 60 seconds, and then rinse with water for 30 seconds to perform pattern processing.
  • the patterned substrate was post-baked at 230 ° C. for 60 minutes (in air) using an oven to prepare a cured film of a positive photosensitive resin composition.
  • the laminated substrate (A) shown in FIG. 1 was prepared using the positive photosensitive resin composition and the silver ink material ( ⁇ ).
  • the base material 1 is a glass substrate obtained by sputtering SiO 2 on the surface
  • the opaque wiring electrode layer 2 is a conductive pattern layer made of a silver ink material ( ⁇ )
  • the light shielding layer 3 is a cured film made of a positive photosensitive resin composition. Is.
  • the portion of the laminated substrate (A) corresponding to the pad portion 6 was immersed in PGMEA at 100 ° C. for 10 minutes, washed with water for 1 minute, and then the image magnified 50 times was observed with an optical microscope. The appearance of the cured film before and after immersion was observed to evaluate the solvent resistance. 2: No change in appearance. 1: Cracks occur in the light-shielding layer.
  • the laminated substrate (B) shown in FIGS. 2 and 5 was prepared using the positive photosensitive resin composition, the silver ink material ( ⁇ ), and the photosensitive insulating material ( ⁇ ).
  • the base material 1 is a glass substrate obtained by sputtering SiO 2 on the surface
  • the opaque wiring electrode layer 2 is a conductive pattern layer made of a silver ink material ( ⁇ )
  • the light shielding layer 3 is a cured film made of a positive photosensitive resin composition.
  • the insulating layer 4 is an insulating layer made of a photosensitive insulating material ( ⁇ ).
  • the residue on the substrate was evaluated by the transmittance evaluation of the exposed portion of the positive photosensitive resin composition on the insulating layer 4 of the laminated substrate shown in FIG. ..
  • the transmittance at 400 nm before and after the formation of the light-shielding film is measured by the ultraviolet-visible spectrophotometer Shimadzu Corporation. The measurement was carried out using "MultiSpec-1500 (trade name)" manufactured by Mfg. Co., Ltd.
  • the laminated substrate (B) was evaluated for migration resistance under high temperature and high humidity.
  • the insulation deterioration characteristic evaluation system "ETAC SIR13" manufactured by Kusumoto Kasei Co., Ltd. was used for the measurement. Electrodes were attached to the connection portions of the opaque wiring electrodes 2, and the samples were placed in a high-temperature and high-humidity tank set to 85 ° C. and 85% RH conditions. After 5 minutes had passed since the environment in the tank became stable, a voltage was applied between the electrodes of the opaque wiring electrode 2 and the change with time of the insulation resistance was measured.
  • a voltage of 5 V was applied with the opaque wiring electrode of the first layer as the positive electrode and the opaque wiring electrode of the second layer as the negative electrode, and the resistance value was measured at 5-minute intervals for 1000 hours.
  • the measured resistance value reached 10 to the 5th power ⁇ or less, it was judged as a short circuit due to poor insulation, and the printing pressure was stopped, and the test time up to that point was defined as the short circuit time.
  • Migration resistance was evaluated according to the following evaluation criteria. 2 or more was passed. 3: Short circuit time is 1000 hours or more 2: Short circuit time is 280 hours or more and less than 1000 hours 1: Short circuit time is less than 280 hours.
  • Example 1 First, MA-100: 3.00 g as the colorant (C), BYK-21116: 1.00 g as the dispersant, PGMEA: 40.00 g, DPM: 20.00 g with a homogenizer at 1200 rpm for 30 minutes. The mixture was mixed and further dispersed using a high-pressure wet medialess atomizer Nanomizer (Namizer Co., Ltd.) to obtain a dispersion. With respect to 64.00 g of this dispersion, under a yellow lamp, the photosensitizer (b-1) was 3.00 g, the cross-linking agent was MX-270: 0.69 g, and the solvent was PGMEA: 14.
  • Examples 2 to 29, Comparative Examples 1 to 5 Positive photosensitive resin compositions having the compositions shown in Tables 1 to 4 were obtained by the same method as in Example 1, and each positive photosensitive resin composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Tables 5-8.
  • the application of the cured film obtained by curing the photosensitive resin composition of the present invention is not particularly limited, but for example, light-shielding such as a light-shielding layer of an opaque electrode for a touch panel, a black matrix of a color filter, or a black column spacer of a liquid crystal display. It is suitably used as a film, a pixel dividing layer of an organic EL display device, a TFT flattening layer, or the like.

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