WO2015159655A1 - 感光性樹脂組成物、導電性パターンの製造方法、基板、素子およびタッチパネル - Google Patents
感光性樹脂組成物、導電性パターンの製造方法、基板、素子およびタッチパネル Download PDFInfo
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- WO2015159655A1 WO2015159655A1 PCT/JP2015/058860 JP2015058860W WO2015159655A1 WO 2015159655 A1 WO2015159655 A1 WO 2015159655A1 JP 2015058860 W JP2015058860 W JP 2015058860W WO 2015159655 A1 WO2015159655 A1 WO 2015159655A1
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- 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
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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
- G03F7/16—Coating processes; Apparatus therefor
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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
- G03F7/16—Coating processes; Apparatus therefor
- G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
Definitions
- the present invention relates to a photosensitive resin composition, a method for producing a conductive pattern, a substrate, an element, and a touch panel.
- a method for producing a conductive pattern used for electronic wiring by using a resin composition containing conductive particles the conductive particles are brought into contact by heating and firing after the pattern is formed on the substrate.
- a method for obtaining a sex pattern is common.
- Examples of a method for forming a pattern on a substrate include a screen printing method, an ink jet method, and a photolithography method.
- the screen printing method and the ink jet method are not suitable for forming a fine pattern.
- a photolithography method is suitable for the formation.
- the photolithography method is a method of forming an exposed portion and an unexposed portion on a coating film by irradiating ultraviolet rays or the like through a photomask on which the shape of a fine wiring pattern is drawn after application and drying of the photosensitive composition. By developing it with a developer, a fine pattern is formed on the substrate. And it is a method of forming a fine electroconductive pattern by subsequent electroconductivity processing.
- the photosensitive composition used in this method is composed of conductive particles, a photosensitive agent, a resin, and the like (Patent Document 1).
- the fine particles have the ability to move atoms on the surface. When the particles come into contact with each other, the particles are likely to be fused easily, which is advantageous for lowering the process temperature.
- the fusion of the metal fine particles proceeds even near room temperature, and the composition produced using particles having a particle size that is easy to fuse deteriorates the applicability or photosensitivity due to the presence of large size fused particles. There are things to do.
- surface coating of various metal fine particles is performed for the purpose of suppressing contact between the metal fine particles and preventing fusion.
- Patent Documents 2 and 3 As a method for surface coating of metal fine particles, organic coating in the liquid phase is actively performed.
- silver fine particles Patent Documents 2 and 3
- Coated silver fine particles Patent Document 4 and the like are known.
- the present invention was devised in view of the drawbacks of the related art, and the object of the present invention is to provide a photosensitive resin composition capable of achieving both fine pattern resolution and conductivity after heat treatment. Is to provide. By using such a photosensitive resin composition, a high-definition conductive pattern can be obtained.
- the present inventors have introduced a necessary amount of a photosensitizer and resin to express photosensitivity, that is, resolution of a fine pattern, and after heat treatment, a part or all of components other than conductive particles It was found that by decomposing, the concentration of conductive particles in the total solid content is increased and conductivity is exhibited, thereby solving the above problem.
- the present invention provides a photosensitive resin composition containing (A) conductive fine particles surface-coated with a carbon simple substance and / or a carbon compound, and (B) an alkali-soluble resin having an acid-dissociable group.
- the photosensitive resin composition of the present invention has high sensitivity in exposure even after long-term storage at room temperature, and is excellent in resolution after pattern formation. Moreover, by heating in the air after exposure and development, the acid dissociable group in the resin is released, the volume shrinkage of the resin is increased, and the ratio of the conductive fine particles is increased. Furthermore, in the surface-coated conductive fine particles, the surface coating layer is thermally oxidatively decomposed by oxygen in the air, the fusion of the conductive fine particles is promoted, and a cured film pattern having excellent conductivity can be obtained.
- the photosensitive resin composition of the present invention is a composition containing (A) conductive fine particles whose surface is coated with a carbon simple substance and / or a carbon compound, and (B) an alkali-soluble resin having an acid-dissociable group.
- the photosensitivity in this composition may be positive photosensitivity or negative photosensitivity, but is preferably negative photosensitivity.
- Conductive fine particles As the conductive fine particles in the conductive fine particles whose surface is coated with a carbon simple substance and / or a carbon compound, for example, gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin ( Examples thereof include fine metal particles such as Sn), bismuth (Bi), lead (Pb), zinc (Zn), palladium (Pd), platinum (Pt), aluminum (Al), tungsten (W) or molybdenum (Mo). It is preferably a metal fine particle containing at least one element selected from the group consisting of gold, silver, copper, nickel, tin, bismuth, lead, zinc, palladium, platinum, aluminum and carbon. More preferably.
- a gas phase reaction method is preferable, and a thermal plasma method with high productivity is more preferable.
- the method for generating thermal plasma include arc discharge, high-frequency plasma, and hybrid plasma, but high-frequency plasma that contains less impurities from the electrode is preferable.
- the particle diameter of the conductive fine particles is preferably 10 to 100 nm and more preferably 10 to 60 nm in order to facilitate formation of a fine pattern having desired conductivity.
- the particle diameter of the conductive fine particles refers to the specific surface area equivalent diameter (Dp) of the conductive fine particles.
- the specific surface area equivalent diameter (Dp) is the total surface area of individual particles contained in a unit mass of powder. Assuming that the individual particles contained in the powder are spherical with the same diameter, the specific surface area equivalent diameter Dp is calculated by the following equation.
- the specific surface area equivalent diameter (particle diameter) is Dp ( ⁇ m)
- the density of spherical particles is ⁇
- the specific surface area of spherical particles is Sw (m 2 / g)
- Dp 6 / ( ⁇ Sw)
- the specific surface area Sw (m 2 / g) (BET value) of the powder can be measured with a fully automatic specific surface area measuring apparatus (for example, Macsorb HMmodel-1201; manufactured by Mountaintech Co., Ltd.).
- a surface treatment method for example, a method of contacting with a reactive gas when producing conductive fine particles by a thermal plasma method (Japanese Patent Laid-Open No. 2007-138287) can be mentioned.
- the surface of the conductive fine particles is preferably completely covered, but the coating is intended to prevent fusion of the conductive fine particles at a low temperature, so long as this object is achieved. In the case of the present invention, it is allowed that particles having a partially incomplete coating exist.
- the average thickness of the surface coating layer improves the fine pattern processability by suppressing the fusion of the conductive fine particles, and expresses the desired conductivity by heat treatment at a temperature of 300 ° C. or lower. 0.1 to 10 nm is preferable.
- the average thickness of the surface coating layer is determined by measuring the mass loss of the conductive fine particles surface-coated with a carbon simple substance and / or carbon compound by a thermobalance, assuming that all values are due to carbon combustion, and from the particle diameter
- the average thickness of the surface coating layer can be calculated with a carbon density of 2.0. It is assumed that carbon is coated with an average thickness A ( ⁇ m) on conductive fine particles whose particle diameter (Dp) is known. Let n be the number of particles coated with carbon.
- the content of the conductive fine particles whose surface is coated with (A) the carbon simple substance and / or the carbon compound in the photosensitive resin composition is such that the residual organic component does not interfere with the contact between the conductive fine particles, and the desired conductivity.
- it is preferably 70 to 95% by mass, more preferably 75 to 95% by mass, and more preferably 75% to 75% by mass with respect to the total solid content in the composition. More preferably, it is -90 mass%.
- the total solid content means all components excluding the solvent among the components contained in the photosensitive resin composition.
- the alkali-soluble resin having an acid-dissociable group is generally obtained by copolymerizing a compound having a carboxyl group and a compound having an acid-dissociable group. More specific examples include copolymerization of a (meth) acrylic acid compound containing a carboxyl group and a (meth) acrylic acid ester having an acid dissociable group. In this case, an acrylic resin having an acid dissociable group is obtained. Since this acrylic resin has a carboxyl group in the side chain, it is alkali-soluble.
- a vinyl aromatic compound or an amide-based resin in addition to a (meth) acrylic acid compound having a carboxyl group or a (meth) acrylic acid ester having an acid-dissociable group, a vinyl aromatic compound or an amide-based resin can be used. Those obtained by radical polymerization of monomers such as saturated compounds or other vinyl compounds are preferred.
- an azo compound such as azobisisobutyronitrile or an organic peroxide such as benzoyl peroxide is generally used.
- the conditions for radical polymerization can be set as appropriate.
- (meth) acrylic acid, (meth) acrylic acid ester and a radical polymerization catalyst are added to the solvent, and the inside of the reaction vessel is sufficiently filled by bubbling or vacuum degassing. It is preferable to carry out the reaction at 60 to 110 ° C. for 30 to 300 minutes after nitrogen substitution.
- chain transfer agents such as a thiol compound, as needed.
- Examples of the (meth) acrylic acid compound having a carboxyl group include (meth) acrylic acid, itaconic acid, maleic acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl hexahydro.
- Examples include phthalic acid or 2- (meth) acryloyloxyethyl phthalic acid.
- Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) Cyclohexyl acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, (meth) 2-cyclohexyloxycarbonylethyl acrylate, 2-cyclohexylenylcarbonyl (meth) acrylate, 2- (4-methoxycyclohexyl) oxycarbonylethyl (meth) acrylate, norbornyl (meth) acrylate, (meth Iso
- vinyl aromatic compound examples include aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and ⁇ -methylstyrene.
- amide unsaturated compound examples include (meth) acrylamide, N-methylolacrylamide, and N-vinylpyrrolidone.
- Examples of other vinyl compounds include (meth) acrylonitrile, allyl alcohol, vinyl acetate, cyclohexyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, 2-hydroxy vinyl ether, or 4 -Hydroxy vinyl ethers.
- the acid dissociable group is preferably an organic group having 4 to 15 carbon atoms, more preferably an organic group having 6 to 15 carbon atoms.
- the number of carbon atoms of the acid dissociable group is less than 4, vaporization occurs at a low temperature after desorption, so that large bubbles are generated in the film, preventing contact between the conductive fine particles, and conductivity may be deteriorated.
- the number of carbon atoms of the acid dissociable group exceeds 15, the dissociable group remains in the film after desorption, thereby preventing contact between the conductive fine particles, and the conductivity may also deteriorate.
- the acid-dissociable group of the acid-dissociable group is an organic group having 6 to 15 carbon atoms, even if bubbles are generated in the film, they can be easily eliminated by post-baking and have good conductivity. A conductive pattern can be formed.
- Examples of the acid dissociable group include a tert-butyl group, a tert-butoxycarbonyl group, a benzyl group, a methyladamantyl group, and a tetrahydropyranyl group.
- Examples of the (meth) acrylic acid ester having an acid dissociable group include 1-methyladamantyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butoxycarbonyl (meth) acrylate, and (meth) acrylic.
- Examples include benzyl acid or tetrahydropyranyl (meth) acrylate.
- the content of the (B) acid-dissociable group-containing alkali-soluble resin is within the range of 10 to 30% by mass with respect to the total solid content in consideration of the expression of photosensitivity. Is preferred.
- the alkali-soluble resin having an acid dissociable group is preferably an alkali-soluble resin obtained by radical copolymerization of a compound having an acid dissociable group in an amount of 20 to 80 mol%.
- (meth) acrylic acid ester having an acid dissociable group is preferably contained in an alkali-soluble resin as a monomer component in an amount of 20 to 80 mol%.
- the alkali-soluble resin having an acid dissociable group preferably contains a radical polymerizable group from the viewpoint of improving the high resolution and the development margin.
- the alkali-soluble resin having an acid-dissociable group does not contain a radically polymerizable group, the development margin may be insufficient and a high-resolution pattern may not be obtained.
- the resin having a carboxyl group it is preferable to react a part of the carboxyl group in the resin having a carboxyl group with the epoxy group in the monosubstituted epoxy compound having a radical polymerizable group.
- the resin having a carboxyl group an acrylic resin having a carboxyl group is preferable.
- photo radical polymerization becomes possible.
- the radically polymerizable group is preferably a (meth) acryloyl group having high photoradical polymerization reactivity.
- Examples of the catalyst used for the addition reaction of the monosubstituted epoxy compound having a radical polymerizable group include amino catalysts such as dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, dimethylbenzylamine, 2-ethyl Tin-based catalysts such as tin (II) hexanoate or dibutyltin laurate, titanium-based catalysts such as titanium 2-ethylhexanoate (IV), phosphorus-based catalysts such as triphenylphosphine, acetylacetonate chromium or chromium chloride A chromium-based catalyst is mentioned.
- amino catalysts such as dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, dimethylbenzylamine, 2-ethyl Tin-based catalysts such as tin (II) hexanoate or dibutyltin laurate
- titanium-based catalysts such as titanium 2-eth
- Examples of the monosubstituted epoxy compound having a radical polymerizable group include glycidyl (meth) acrylate, 2- (glycidyloxy) ethyl (meth) acrylate, 3- (glycidyloxy) propyl (meth) acrylate, (meth) ) 4- (glycidyloxy) butyl acrylate, 4,5-epoxypentyl (meth) acrylate, (meth) acrylic acid-5,6-epoxyhexyl, (meth) acrylic acid-6,7-epoxyheptyl, allyl Glycidyl ether, vinyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, ⁇ -methyl-o-vinylbenzyl glycidyl ether, ⁇ -methyl
- glycidyl (meth) acrylate 2- (glycidyloxy) ethyl (meth) acrylate, (meth) ) 3- (Glycidyloxy) propyl acrylate or (meta 4- acrylate (glycidyloxy) butyl are preferred.
- the carboxylic acid equivalent of the acrylic resin obtained by reacting an acrylic resin having a carboxyl group and an acid dissociable group with a monosubstituted epoxy compound having a radical polymerizable group is preferably 200 to 1,400 g / mol, preferably 400 to 1,000 g / mol is more preferable.
- the carboxylic acid equivalent of the acrylic resin can be calculated by measuring the acid value.
- the double bond equivalent of an acrylic resin obtained by reacting an acrylic resin having a carboxyl group and an acid-dissociable group with a mono-substituted epoxy compound having a radical polymerizable group achieves both a high level of hardness and crack resistance. Therefore, it is preferably 150 to 10,000 g / mol.
- the double bond equivalent of the acrylic resin can be calculated by measuring the iodine value.
- the weight average molecular weight (Mw) of an acrylic resin obtained by reacting an acrylic resin having a carboxyl group and an acid dissociable group with a mono-substituted epoxy compound having a radical polymerizable group is measured by gel permeation chromatography (GPC). It is preferably 1,000 to 100,000 in terms of polystyrene.
- the photosensitive resin composition of the present invention may contain (C) a dispersant.
- C By containing a dispersing agent, the electroconductive fine particle surface-coated by (A) carbon simple substance and / or a carbon compound can be made to exist stably in the photosensitive resin composition.
- the dispersant is preferably an amine-based one.
- examples of commercially available amine-based (C) dispersants include DISPERBYK 106, 108, 112, 116, 142, 145, 166, 180, 2001, 2008, 2022, 2150, 6919, or 21116 (all of which are Big Chemie Japan). Or Efka 4300, 4400, 4401, 4403, 4406, 4510, 4570, 4800, 5054, 5055, or 5207 (all of which are manufactured by BASF).
- the (C) dispersant preferably has an acrylic block copolymer structure.
- examples of the commercially available amine-based (C) dispersant having an acrylic block copolymer structure include DISPERBYK2001, 2008, 2022, 2150, 6919, or 21116, or Efka4300.
- the content of the (C) dispersant in the photosensitive resin composition is such that the dispersion of the conductive fine particles is good, finer pattern processing is possible, the contact and fusion of the conductive fine particles are advanced, and higher conductivity is achieved.
- 1 to 7 parts by mass is preferable with respect to 100 parts by mass in total of (A) conductive fine particles and other particles described later.
- the photosensitive resin composition of the present invention may contain (D) a photopolymerization initiator.
- D By containing a photoinitiator, negative photosensitive property can be provided to the photosensitive resin composition.
- Examples of the photopolymerization initiator (D) include acetophenone compounds, benzophenone compounds, benzoin ether compounds, ⁇ -aminoalkylphenone compounds, thioxanthone compounds, organic peroxides, imidazole compounds, titanocene compounds, Examples include triazine compounds, acylphosphine oxide compounds, quinone compounds, or oxime ester compounds, but oxime ester compounds that have high sensitivity even when added in a small amount are preferable, and oxime ester compounds having a carbazole skeleton are more preferable. .
- Examples of the oxime ester compound having no carbazole skeleton include Irgacure OXE 01 (manufactured by BASF), and examples of the oxime ester compound having a carbazole skeleton include Irgacure OXE02 (manufactured by BASF), Adeka. Optomer N1919 (manufactured by ADEKA Corporation) or Adeka Arcles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
- the photosensitive resin composition of the present invention may contain (E) a solvent.
- Solvents include, for example, propylene glycol monomethyl ether, propylene glycol monobutyl ether, 2-heptanol, cyclohexanol, cyclopentanol, 2-butanol, 2-pentanol, t-butanol, diacetone alcohol, ⁇ -terpineol , Methyl 2-hydroxyisoisobutyrate, ethyl 2-hydroxyisoisobutyrate, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl acetoacetate, methyl-3-methoxypropionate, 3-methyl-3-methoxybutylacetate, cyclo Pentanone, cyclohexanone, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, benzyl acetate, ethyl benzoate, diethyl ox
- the photosensitive resin composition of the present invention may contain other particles (A) other than conductive fine particles whose surface is coated with a carbon simple substance and / or a carbon compound for the purpose of improving dispersibility and controlling conductivity. I do not care.
- the other particles include metal fine particles or metal oxide fine particles, organic pigments, and inorganic pigments that are not surface-coated.
- the particle diameter of these other particles is preferably 10 to 100 nm.
- the particle diameter is less than 10 nm, the use of a dispersant for stabilizing the dispersion increases, and it may be difficult to obtain desired conductivity.
- the particle diameter exceeds 100 nm, the resolution of the pattern is lowered, and it may be difficult to form an ultrafine pattern of 5 ⁇ m or less.
- carbon black (C) which can be used in combination with a dispersant and contributes to conductivity control is preferable.
- Examples of carbon black include MA77, 7, 8, 11, 100, 100R, 100S, 230, 220, or 14 (all of which are manufactured by Mitsubishi Chemical Corporation), # 52, 47, 45, 45L, 44, 40. 33, 32, 30, 25, 20, 10, 5, 95, 85 or 260 (all are manufactured by Mitsubishi Chemical Corporation), Special Black 100, 250, 350 or 550 (all are manufactured by Evonik Degussa) Or Printex95, 90, 55, 45, 40, P, 60, L6, L, 300, 30, ES23, 9, ES22, 35, 25, 200, A or G (all of which are manufactured by Evonik Degussa) MA77, 7, 8, 11, 100, 100R, 100 having a pH value of 4 or less , 230, 220 or 14 or Special Black100,250,350 or 550 are preferred.
- the pH value of carbon black can be measured according to JIS K5101.
- the photosensitive resin composition of the present invention may contain (F) a photoacid generator and / or a thermal acid generator.
- the generated acid promotes the decomposition of the acid dissociable group in the alkali-soluble resin (B) having an acid dissociable group, and the heat treatment temperature under air can be lowered.
- thermal acid generator that is a compound that generates an acid by heat
- examples of the thermal acid generator that is a compound that generates an acid by heat include SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI-150L, SI-160L, SI-180L or SI-200 (all of which are manufactured by Sanshin Chemical Industry Co., Ltd.), 4-hydroxyphenyldimethylsulfonium, benzyl -4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium or 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium or their methanesulfonic acid Salt, trifluoromethane Examples include sulfonate, camphorsulfonate, or p-toluen
- the content of the thermal acid generator in the photosensitive resin composition is as follows: (B) The decomposition of the acid dissociable group in the alkali-soluble resin having an acid dissociable group content is promoted and the contact between the conductive fine particles is prevented. In order to obtain higher conductivity, 0.01 to 3 parts by mass is preferable with respect to 100 parts by mass of the (B) alkali-soluble resin having an acid dissociable group.
- the acid generated from the photoacid generator which is a compound that generates an acid by light, promotes the decomposition of the acid dissociable group in the alkali-soluble resin having an acid dissociable group (B). Strong acids such as p-toluenesulfonic acid are preferred.
- Examples of the photoacid generator include SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-100, NAI-1002, NAI-1003, and NAI. -1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106 or PAI-1001 (All as above, manufactured by Midori Chemical Co., Ltd.), SP-077 or SP-082 (all as described above, manufactured by ADEKA), TPS-PFBS (manufactured by Toyo Gosei Co., Ltd.), CGI-MDT or CGI -NIT (all of which are manufactured by Ciba Japan) or WPAG-281, WPAG-336, WPA -339, WPAG-342, WPAG-344, WPAG-350, WPAG-370, W
- the content of the photoacid generator in the photosensitive resin composition is (B) promotes the decomposition of the acid dissociable group in the alkali-soluble resin having an acid dissociable group, and does not hinder the contact between the conductive fine particles.
- 0.01 to 5 parts by mass is preferable with respect to 100 parts by mass of (B) the alkali-soluble resin having an acid dissociable group.
- a thermal acid generator and a photoacid generator may be used in combination.
- the photosensitive resin composition of the present invention contains (F) a photoacid generator
- the photosensitive resin composition may further contain a sensitizer.
- the sensitizer is preferably vaporized by heat treatment or discolored by light irradiation even when remaining in the cured film, and more preferably discolored by light irradiation from the viewpoint of high resolution in pattern processing. preferable.
- coumarin such as 3,3′-carbonylbis (diethylaminocoumarin)
- anthraquinone such as 9,10-anthraquinone
- benzophenone 4,4 ′.
- -Aromatic ketones such as dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone or benzaldehyde or biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, pyrene, anthracene, 9-phenylanthracene, 9-methoxyanthracene 9,10-diphenylanthracene, 9,10-bis (4-methoxyphenyl) anthracene, 9,10-bis (triphenylsilyl) anthracene, 9,10-dimethoxyanthracene 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene (DPA; manufactured by Kawasaki Kasei Co., Ltd.), 9,10-dibutoxyanthracene (DBA; manufactured by Kawasaki Kasei Co., Ltd.), 9,10- Examples thereof include conden
- the sensitizer that is vaporized by heat treatment a sensitizer that sublimates, evaporates, or thermally decomposed by thermal decomposition sublimates or evaporates by heat treatment is preferable.
- the vaporization temperature of the sensitizer is preferably 150 to 300 ° C. because it does not vaporize at the pre-baking temperature, but decomposes and vaporizes at the time of thermosetting to contact and fuse the conductive fine particles.
- the sensitizer is preferably an anthracene-based compound from the viewpoint that high sensitivity and high resolution can be achieved, and dimerization and fading by light irradiation, and is stable to heat.
- 9,10-disubstituted An anthracene compound is preferable, and from the viewpoint of improving the solubility of the sensitizer and the reactivity of the photodimerization reaction, the 9,10-dialkoxy anthracene compound represented by the general formula (1) is preferable. Further preferred.
- R 1 ⁇ R 8 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, an ethynyl group, an aryl group or an acyl group or an organic group to which they are substituted
- R 9 And R 10 each independently represents an alkoxy group having 1 to 20 carbon atoms or an alkoxy group substituted with another organic group.
- Examples of the alkyl group for R 1 to R 8 include a methyl group, an ethyl group, and an n-propyl group.
- the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentyloxy group.
- Examples of the alkenyl group include a vinyl group, an acryloxypropyl group, and a methacryloxypropyl group.
- Examples of the aryl group include a phenyl group, a tolyl group, and a naphthyl group.
- Examples of the acyl group include an acetyl group.
- R 1 to R 8 are preferably hydrogen or an organic group having 1 to 6 carbon atoms, and R 1 , R 4 , R 5 and R 8 More preferably, is hydrogen.
- Examples of the substituent that substitutes the alkoxy group in R 9 and R 10 include an alkoxy group and an acyl group.
- Examples of the alkoxy group in this case include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, methoxyethoxy group, 1-methoxy-2-propoxy group or 1-acetyl-2-propoxy group.
- a propoxy group or a butoxy group is preferable from the viewpoint of the solubility of the compound and the color fading reaction due to photodimerization.
- the sensitization effect for photosensitizing the photoacid generator is sufficient, the contact between the conductive fine particles is not hindered, and higher conductivity is obtained ( B) 0.001 to 5 parts by mass is preferable with respect to 100 parts by mass of the alkali-soluble resin having an acid dissociable group, and 0.005 to 1 part by mass is more preferable.
- the photosensitive resin composition of the present invention may contain (X) a pigment and / or dye that absorbs visible light as long as the contact and fusion between the conductive fine particles are not inhibited. Since the photosensitive resin composition contains X) a pigment and / or dye that absorbs visible light, it is possible to suppress visible light reflection of the conductive pattern after post-baking.
- pigments that absorb visible light include lactam pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, diaminoanthraquinone pigments, dioxazine pigments, indanthrone pigments, carbon black, and inorganic pigments. It is done.
- blue pigments include C.I. I. Pigment blue (hereinafter “PB”) 15, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, PB16 or PB60.
- purple pigments include C.I. I. Pigment Violet (hereinafter “PV”) 19, PV23 or PV37.
- red pigments include C.I. I. Pigment red (hereinafter “PR”) 149, PR166, PR177, PR179, PR209, or PR254.
- the green pigment include C.I. I. Pigment green (hereinafter “PG”) 7, PG36 or PG58.
- yellow pigments include C.I. I.
- Pigment yellow (hereinafter “PY”) 150, PY138, PY139, or PY185.
- the black pigment include furnace black such as HCF, MCF, LFF, RCF, SAF, ISAF, HAF, XCF, FEF, GPF or SRF, thermal black such as FT or MT, carbon such as channel black or acetylene black.
- black or lactam pigments for example, “Irgaphor” (registered trademark) black S0100CF; manufactured by BASF).
- carbon black excellent in heat resistance, light resistance and visible light absorption is preferable, and furnace black or lactam pigment is more preferable from the viewpoint of conductivity and dispersibility.
- Examples of carbon black include MA77, 7, 8, 11, 100, 100R, 100S, 230, 220, or 14 (all of which are manufactured by Mitsubishi Chemical Corporation), # 52, 47, 45, 45L, 44, 40. 33, 32, 30, 25, 20, 10, 5, 95, 85 or 260 (all are manufactured by Mitsubishi Chemical Corporation), Special Black 100, 250, 350 or 550 (all are manufactured by Evonik Degussa) Or Printex95, 90, 55, 45, 40, P, 60, L6, L, 300, 30, ES23, 9, ES22, 35, 25, 200, A or G, but the pH value is 4 or less MA77, 7, 8, 11, 100, 100R, 100S, 230, 220 or 14 or S ecial Black100,250,350 or 550 is preferable.
- the pH value of carbon black can be measured according to JIS K5101.
- the addition amount of the pigment having absorption in visible light in the photosensitive resin composition is preferably 2 to 30 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin having an acid dissociable group.
- dyes that absorb visible light include, for example, ferrocene dyes, fluorenone dyes, perylene dyes, triphenylmethane dyes, coumarin dyes, diphenylamine dyes, quinacridone dyes, quinophthalone dyes, phthalocyanine dyes or Xanthene-based dyes can be mentioned, and black dyes excellent in heat resistance, light resistance and visible light absorption are preferable, and VALIFAST Black 1888, VALIFAST Black 3830, NUbian Black PA-2802 or OIL Black 860 are preferable.
- the addition amount of the dye having absorption in visible light in the photosensitive resin composition is preferably 2 to 40 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin having an acid dissociable group.
- the photosensitive resin composition of the present invention can be prepared by bringing the acrylic monomer or other acrylic polymer having no acid dissociable group into contact between the conductive fine particles and You may contain in the range which does not inhibit a melt
- acrylic monomer examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or di Pentaerythritol penta (meth) acrylate or an alkyl modified product, an alkyl ether modified product or an alkyl ester modified product thereof may be mentioned.
- acrylic polymer having no acid dissociable group examples include SIRIUS-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), which is a polyfunctional acrylate having a dendrimer structure.
- the photosensitive resin composition of the present invention may further contain an adhesion improver, a surfactant, a polymerization inhibitor or the like, if necessary.
- adhesion improving agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl
- silane coupling agents such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
- the surfactant examples include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene alkyl ether sulfate triethanolamine, a cationic surfactant such as stearylamine acetate or lauryltrimethylammonium chloride, lauryldimethylamine oxide, or lauryl.
- Amphoteric surfactants such as carboxymethylhydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether or sorbitan monostearate, fluorosurfactants or silicon surfactants Is mentioned.
- the addition amount of the surfactant in the photosensitive resin composition is preferably 0.001 to 10% by mass with respect to the entire composition in order to improve the coating property and the uniformity of the coating film surface. More preferably, it is ⁇ 1% by mass. When the addition amount is less than 0.001% by mass, the effect of coating property and coating surface uniformity may be insufficient. On the other hand, when the addition amount exceeds 10% by mass, coating film defects such as cissing and dents and particle aggregation may occur.
- polymerization inhibitor examples include hydroquinone-based, catechol-based, phosphorus-based, sulfur-based, amine-based or hindered phenol-based compounds.
- hydroquinone-based and catechol-based compounds are dissolved in a solvent.
- Hydroquinone or catechol-based compounds that do not impair the properties and dispersion stability of the pigment are preferred.
- Hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2, 5-bis (1,1-dimethylbutyl) hydroquinone, catechol or tert-butylcatechol is more preferred.
- the photosensitive resin composition of the present invention may be produced by directly dispersing conductive fine particles in a resin solution using a disperser, but it is difficult to uniformly disperse conductive fine particles. Then, using a dispersant, a dispersion liquid in which conductive fine particles are dispersed in an organic solvent is prepared in advance, and this dispersion liquid is a solution containing a monomer, a polymer, an adhesion improver, a surfactant, a polymerization inhibitor, and the like. It is preferable to manufacture by the method of mixing with.
- the surface-coated silver fine particle dispersion is preferably dispersed using a mild disperser or a medialess disperser, and is dispersed using a medialess disperser. Is more preferable.
- the surface-coated silver fine particle dispersion can be produced by dispersing silver fine particles in an organic solvent using a disperser such as a mild disperser nanogetter or a high-pressure wet medialess atomizer nanomizer). it can.
- a dispersion method such as a ball mill, a sand grinder, a three-roll mill, or a high-speed impact mill may damage the surface coating layer of silver fine particles and promote the fusion of silver fine particles.
- the method for producing a conductive pattern of the present invention comprises a coating step of applying the photosensitive resin composition of the present invention on a substrate surface, a pre-baking step of drying the same, a step of exposing and developing it to form a pattern (exposure) Step, development step) and a post-baking step for post-baking the same.
- Examples of the substrate used in the coating process include a silicon wafer, a ceramic substrate, and an organic substrate.
- the ceramic substrate include glass substrates such as soda glass, non-alkali glass, borosilicate glass, and quartz glass, alumina substrates, aluminum nitride substrates, and silicon carbide substrates.
- the organic substrate include an epoxy substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, a polyimide film, and a polyester film.
- Examples of the method for coating the photosensitive resin composition of the present invention on a substrate surface include coating using a spin coater, bar coater, blade coater, roll coater, die coater, calendar coater or meniscus coater, screen printing, and spraying. Application or dip coating may be mentioned.
- drying method in the pre-baking step examples include hot plate, hot air dryer (oven), vacuum drying, vacuum drying, and drying by infrared irradiation.
- the prebaking temperature and time may be appropriately determined depending on the composition of the photosensitive resin composition and the thickness of the coating film to be dried, but it is preferably heated at a temperature range of 50 to 150 ° C. for 10 seconds to 30 minutes.
- the ultimate pressure for drying under reduced pressure is preferably 10 to 200 Pa, more preferably 30 to 100 Pa.
- the light source used in the exposure process for example, j-line, i-line, h-line or g-line of a mercury lamp is preferable.
- alkaline substance used for the alkaline developer in the development step examples include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, or aqueous ammonia, ethylamine, or n-propyl.
- inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, or aqueous ammonia, ethylamine, or n-propyl.
- Primary amines such as amines, secondary amines such as diethylamine or di-n-propylamine, tertiary amines such as triethylamine or methyldiethylamine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide (TMAH) , Quaternary ammonium salts such as choline, triethanolamine, diethanolamine, monoethanolamine, alcoholamines such as dimethylaminoethanol or diethylaminoethanol, or pyro And organic alkalis such as cyclic amines such as pyridine, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene, 1,5-diazabicyclo [4,3,0] -5-nonane or morpholine.
- a water-soluble organic solvent such as ethanol, ⁇ -butyrolactone, dimethylformamide, or N-methyl-2-pyrrolidone may be appropriately added there
- a surfactant such as a nonionic surfactant to these alkaline developers.
- drying method in the post-bake process examples include the same as those in the pre-bake process.
- the post-baking atmosphere, temperature and time may be appropriately determined depending on the composition of the photosensitive resin composition and the film thickness of the coating film to be dried, but in the temperature range of 100 to 300 ° C. for 5 to 120 minutes. It is preferable to heat.
- the conductive pattern is formed in a mesh form on the substrate, it can be used as a transparent conductive wiring provided in a touch panel, a display panel such as liquid crystal or organic EL, or an element such as a wearable terminal.
- the conductive pattern is not transparent, if the pattern width is large, the user of the device can visually recognize the wiring. For this reason, it is preferable that the width
- A Conductive fine particles surface-coated with a carbon simple substance and / or a carbon compound
- A-1 Silver fine particles having an average thickness of 1 nm on the surface carbon coating layer and a particle size of 40 nm (manufactured by Nisshin Engineering Co., Ltd.)
- A-2 Silver fine particles whose surface carbon coating layer has an average thickness of 3 nm and a particle diameter of 60 nm (manufactured by Nisshin Engineering Co., Ltd.)
- A-3 Silver fine particles whose surface carbon coating layer has an average thickness of 10 nm and a particle diameter of 100 nm (manufactured by Nisshin Engineering Co., Ltd.)
- A-4) Silver fine particles having an average thickness of the surface carbon coating layer of 0.5 nm and a particle diameter of 50 nm (manufactured by Nisshin Engineering Co., Ltd.)
- A-5 Silver fine particles whose surface carbon coating layer has an average thickness of 0.2 nm and
- a silver homogenizer was used for 85.00 g of silver fine particles (A-1), 4.3 g of dispersant (C-1), and 208.4 g of solvent (E-1).
- a mixing treatment was performed at 1200 rpm for 30 minutes, and the mixed solution was dispersed using a mill type disperser filled with zirconia beads to obtain a silver particle dispersion (A-1-3).
- a homogenizer was used for 70.00 g of silver fine particles (A-1), 3.34 g of dispersant (C-1), and 171.13 g of solvent (E-1).
- a mixing treatment was performed at 1200 rpm for 30 minutes, and the mixed solution was dispersed using a mill type disperser filled with zirconia beads to obtain a silver particle dispersion (A-1-4).
- Silver Fine Particle Dispersion (A-1-5) To 88.00 g of silver fine particles (A-1), 2.61 g of dispersant (C-1) and 211.42 g of solvent (E-1), a homogenizer was used. A mixing treatment was performed at 1200 rpm for 30 minutes, and the mixture was further dispersed using a mill type disperser filled with zirconia beads to obtain a silver particle dispersion (A-1-5).
- a homogenizer was used for 65.00 g of silver fine particles (A-1), 3.32 g of dispersant (C-1), and 159.41 g of solvent (E-1).
- a mixing treatment was performed at 1200 rpm for 30 minutes, and the mixed liquid was further dispersed using a mill-type disperser filled with zirconia beads to obtain a silver particle dispersion (A-1-6).
- a homogenizer was used for 93.00 g of silver fine particles (A-1), 2.61 g of dispersant (C-1) and 223.09 g of solvent (E-1).
- a mixing treatment was performed at 1200 rpm for 30 minutes, and the mixed solution was dispersed using a mill type disperser filled with zirconia beads to obtain a silver particle dispersion (A-1-7).
- Silver Fine Particle Dispersion (A-2-1) Silver fine particles (A-2) 80.00 g, Dispersant (C-1) 4.06 g, Solvent (E-1) 196.14 g A silver fine particle dispersion (A-2-1) was produced in the same manner as the dispersion (A-1-1).
- Silver Fine Particle Dispersion (A-3-1) The above-mentioned silver fine particles were added to 80.00 g of silver fine particles (A-3), 4.06 g of dispersant (C-1) and 196.14 g of solvent (E-1). A silver fine particle dispersion (A-3-1) was produced in the same manner as the dispersion (A-1-1).
- Silver Fine Particle Dispersion (A-4-1) Silver fine particles (A-4) 80.00 g, dispersant (C-1) 4.06 g and solvent (E-1) 196.1 g A silver fine particle dispersion (A-4-1) was produced in the same manner as the dispersion (A-1-1).
- Silver Fine Particle Dispersion (A-5-1) The above silver particles were added to 80.00 g of silver fine particles (A-5), 4.06 g of dispersant (C-1) and 196.1 g of solvent (E-1). A silver fine particle dispersion (A-5-1) was produced in the same manner as the dispersion (A-1-1).
- A-6-1 Preparation of Silver Fine Particle Dispersion (A-6-1) The above silver particles were added to 80.00 g of silver fine particles (A-6), 4.06 g of dispersant (C-1), and 196.1 g of solvent (E-1). A silver fine particle dispersion (A-6-1) was produced in the same manner as the dispersion (A-1-1).
- A-7-1 Preparation of Silver Fine Particle Dispersion (A-7-1) The above silver particles were added to 80.00 g of silver fine particles (A-7), 4.06 g of dispersant (C-1), and 196.1 g of solvent (E-1). A silver fine particle dispersion (A-7-1) was produced in the same manner as the dispersion (A-1-1).
- a homogenizer was used for 80.00 g of silver fine particles (A-1), 4.06 g of dispersant (C-1) and 196.14 g of solvent (E-1). The mixture was subjected to a mixing treatment at 1200 rpm for 30 minutes, and the mixture was dispersed using a mild disperser Nanogetter (Ashizawa Finetech Co., Ltd.) to obtain a silver particle dispersion (A-1-8). It was.
- a homogenizer was used for 75.00 g of silver fine particles (A-1), 3.82 g of dispersant (C-1), and 183.91 g of solvent (E-2). The mixture was subjected to a mixing treatment at 1200 rpm for 30 minutes, and the mixture was dispersed using a high-pressure wet medialess atomizer Nanomizer (Nanomerzer Co., Ltd.) to obtain a silver particle dispersion (A-1-9). Obtained.
- Silver Fine Particle Dispersion (A-2-2) The above-mentioned silver fine particles were added to 80.00 g of silver fine particles (A-2), 4.06 g of dispersant (C-2) and 196.14 g of solvent (E-1). A silver fine particle dispersion (A-2-2) was produced in the same manner as the dispersion (A-1-8).
- A-2-3 Preparation of Silver Fine Particle Dispersion (A-2-3) The above-mentioned silver fine particle dispersion was added to 70 g of silver fine particles (A-2), 3.34 g of dispersant (C-2), and 171.13 g of solvent (E-2). A silver fine particle dispersion (A-2-3) was produced in the same manner as (A-1-9).
- Silver Fine Particle Dispersion (A-4-2) Silver fine particles (A-4) 88.00 g, dispersant (C-2) 2.61 g, and solvent (E-2) 211.42 g A silver fine particle dispersion (A-4-2) was produced in the same manner as the dispersion (A-1-8).
- A-4-3 Preparation of Silver Fine Particle Dispersion (A-4-3) The above-mentioned silver fine particles were added to 65.00 g of silver fine particles (A-4), 3.32 g of dispersant (C-1), and 159.41 g of solvent (E-1). A silver fine particle dispersion (A-4-3) was produced in the same manner as the dispersion (A-1-9).
- Silver Fine Particle Dispersion (A-5-2) The above-mentioned silver fine particles were added to 80.00 g of silver fine particles (A-5), 4.06 g of dispersant (C-1) and 196.14 g of solvent (E-1). A silver fine particle dispersion (A-5-2) was produced in the same manner as the dispersion (A-1-8).
- Silver Fine Particle Dispersion (A-5-3) The above-mentioned silver fine particles were added to 75.00 g of silver fine particles (A-5), 3.82 g of dispersant (C-1), and 183.91 g of solvent (E-2). A silver fine particle dispersion (A-5-3) was produced in the same manner as the dispersion (A-1-9).
- Table 1 and Table 2 summarize the composition of each silver fine particle dispersion produced.
- B-1 2 g of 2,2′-azobis (isobutyronitrile) and PGMEA (propylene glycol methyl ether acetate) were added to a 500 mL flask. 50 g was charged. Thereafter, 23.26 g of methacrylic acid, 31.46
- Table 3 summarizes the composition of each alkali-soluble resin monomer synthesized.
- D Photopolymerization initiator
- D-1 Irgacure OXE02 (oxime ester compound; manufactured by BASF)
- F Photoacid generator and / or thermal acid generator
- F-1 Triphenylsulfonium trifluoromethanesulfonate (onium salt photoacid generator; manufactured by Tokyo Chemical Industry Co., Ltd.)
- F-2) SI-100 thermoal acid generator; manufactured by Sanshin Chemical Industry).
- G Sensitizer (G-1) 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene (DPA; manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
- H Acrylic monomer (H-1) Light acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.)
- X Pigment and / or dye having absorption in visible light
- X-1-1) Pigment dispersion PG58 (“Fastogen” (registered trademark) Green A110; manufactured by DIC Corporation) 80 g
- Dispersant (C-1) 4 0.06 g and solvent (E-2) 84.06 g were mixed with a homogenizer at 1200 rpm for 30 minutes, and the mixture was further dispersed using a mill type disperser filled with zirconia beads.
- a green dispersion (X-1-1) having a solid content of 50% by mass (pigment concentration 47.59% by mass) was obtained.
- Example 1 A patterning property evaluation method will be described by taking Example 1 as an example. First, 4.40 g of 40 mass% alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-2), acrylic monomer (H) with respect to 63.28 g of silver fine particle dispersion (A-1-1). -1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 1.
- each ink was rotated on a non-alkali glass substrate (OA-10; manufactured by Nippon Electric Glass Co., Ltd.) using a spin coater (“1H-360S (trade name)” manufactured by Mikasa Co., Ltd.) at 500 rpm for 10 seconds.
- a pre-baked film with a film thickness of 1 ⁇ m was prepared by pre-baking for 2 minutes at 90 ° C. using a hot plate (SCW-636; manufactured by Dainippon Screen Mfg. Co., Ltd.). did.
- the obtained pre-baked film was exposed with a gap of 100 ⁇ m through a gray scale mask for sensitivity measurement using PLA as an ultrahigh pressure mercury lamp as a light source.
- the film was shower-developed with a 0.045 mass% aqueous potassium hydroxide solution for 90 seconds and then rinsed with water for 30 seconds.
- the exposure amount (hereinafter referred to as “optimum exposure amount”) for forming a 5 ⁇ m line-and-space pattern in a one-to-one width was defined as sensitivity.
- the exposure amount was measured with an I-line illuminometer.
- the amount of development residue between 5 ⁇ m line-and-space patterns at the optimum exposure amount was also confirmed, and evaluation was made in three stages: a large amount of residue, a small amount of residue, and no residue.
- the minimum pattern size after development at the optimum exposure amount was measured and used as the resolution.
- ⁇ Volume resistance evaluation method> The same ink as that used for the above patterning property evaluation was spun on an alkali-free glass substrate using a spin coater (1H-360S; manufactured by Mikasa Co., Ltd.) for 10 seconds at 500 rpm and then for 4 seconds at 1000 rpm. After coating, prebaking was performed at 90 ° C. for 2 minutes using a hot plate to prepare a prebaked film having a thickness of 1 ⁇ m. The resulting pre-baked film was exposed with a gap of 100 ⁇ m through a photomask having a rectangular light transmission pattern (10 mm ⁇ 15 mm) using PLA as a light source with an ultrahigh pressure mercury lamp.
- Example 1 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of the solvent (E-2) and 7.31 g of the solvent (E-1) were added to the mixture of 1.30 g and stirred to prepare ink 1.
- the silver fine particle content based on the total solid content of the ink 1 was 80% by mass.
- Table 4 shows the results of evaluating the patternability and volume resistance by using the ink 1 and the evaluation method described above.
- Example 2 4.63 g of 40% by weight alkali-soluble resin (B-2), 0.41 g of photopolymerization initiator (D-2), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 2) 23.25 g of the solvent (E-2) and 7.31 g of the solvent (E-1) were added to the mixture of 1.30 g and stirred to prepare ink 2.
- the silver fine particle content based on the total solid content of Ink 2 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 3 4.63 g of 40% by mass alkali-soluble resin (B-3), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1)
- Ink 3 was prepared by adding 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) to the mixture of 1.30 g and stirring.
- the silver fine particle content with respect to the total solid content of the ink 3 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 4 4.63 g of 40% by weight alkali-soluble resin (B-4), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 4.
- the silver fine particle content based on the total solid content of the ink 4 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 5 4.63 g of 40% by mass alkali-soluble resin (B-5), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 5.
- the silver fine particle content based on the total solid content of the ink 5 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 6 4.63 g of 40% by weight alkali-soluble resin (B-6), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of the solvent (E-2) and 7.31 g of the solvent (E-1) were added to the mixture of 1.30 g and stirred to prepare ink 6.
- the silver fine particle content based on the total solid content of the ink 6 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 7 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H--) with respect to 63.28 g of silver fine particle dispersion (A-2-1) 1) 23.25 g of the solvent (E-2) and 7.31 g of the solvent (E-1) were added to the mixture of 1.30 g and stirred to prepare ink 7.
- the silver fine particle content based on the total solid content of the ink 7 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 8 4.63 g of 40% by mass alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-3-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 8.
- the silver fine particle content based on the total solid content of the ink 8 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 9 To 63.28 g of silver particle dispersion (A-4-1), 4.40 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H— 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 9. The silver particle content with respect to the total solid content of the ink 9 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 10 To 63.28 g of silver particle dispersion (A-5-1), 4.40 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H— 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 10. The silver particle content based on the total solid content of the ink 10 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 11 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of the solvent (E-2) and 7.31 g of the solvent (E-1) were added to a mixture of 1.30 g and 0.05 g of the photoacid generator (F-1), and the mixture was stirred. Ink 11 was produced. The silver fine particle content based on the total solid content of the ink 11 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 12 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of the solvent (E-2) and 7.31 g of the solvent (E-1) were added to a mixture of 1.30 g and 0.05 g of the photoacid generator (F-2), and the mixture was stirred. Ink 12 was produced. The silver fine particle content based on the total solid content of the ink 12 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 13 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 1.30 g, photoacid generator (F-1) 0.05 g, sensitizer (G-1) 0.001 g mixed with solvent (E-2) 23.25 g, solvent (E-1 Ink 13 was prepared by adding 7.31 g and stirring. The silver fine particle content with respect to the total solid content of the ink 13 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 14 7.37 g of 40 mass% alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 59.33 g of silver fine particle dispersion (A-1-2) 1) 23.25 g of solvent (E-2) and 8.3 g of solvent (E-1) were added to a mixture of 1.30 g and 0.05 g of the photoacid generator (F-1), and the mixture was stirred. Ink 14 was produced. The silver fine particle content with respect to the total solid content of the ink 14 was 75% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 15 To 67.07 g of silver fine particle dispersion (A-1-3), 3.27 g of 40% by mass alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H— 1) 23.25 g of the solvent (E-2) and 5.34 g of the solvent (E-1) were added to a mixture of 0.62 g and 0.05 g of the photoacid generator (F-1) and stirred. Ink 15 was produced. The silver fine particle content relative to the total solid content of the ink 15 was 85% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 16 8.54 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 55.47 g of silver fine particle dispersion (A-1-4) 1) To a mixture of 1.98 g and photoacid generator (F-1) 0.05 g, 23.25 g of solvent (E-2) and 10.30 g of solvent (E-1) were added and stirred. Ink 16 was produced. The silver fine particle content based on the total solid content of the ink 16 was 71% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 17 For 68.00 g of silver fine particle dispersion (A-1-5), 2.92 g of 40% by mass alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H— 1) To a mixture of 0.47 g and 0.05 g of photoacid generator (F-1), 23.25 g of solvent (E-2) and 4.89 g of solvent (E-1) were added and stirred. Ink 17 was produced. The silver fine particle content based on the total solid content of the ink 17 was 88% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 18 1.37 g of 40% by weight alkali-soluble resin (B-1), 0.49 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 71.65 g of silver fine particle dispersion (A-1-7) 1) 23.25 g of solvent (E-2) and 3.28 g of solvent (E-1) were added to a mixture of 0.22 g and stirred to prepare ink 18.
- the silver fine particle content based on the total solid content of the ink 18 was 92% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 19 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-7-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 19.
- the silver fine particle content with respect to the total solid content of the ink 19 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 20 4.63 g of 40% by weight alkali-soluble resin (B-8), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 20.
- the silver fine particle content with respect to the total solid content of the ink 20 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 21 4.63 g of 40% by mass alkali-soluble resin (B-9), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 21.
- the silver fine particle content based on the total solid content of the ink 21 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 22 10.51 g of 40% by weight alkali-soluble resin (B-1), 0.49 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 51.75 g of silver fine particle dispersion (A-1-6) 1) 23.25 g of solvent (E-2) and 11.92 g of solvent (E-1) were added to a mixture of 2.37 g and stirred to prepare ink 22.
- the silver fine particle content based on the total solid content of the ink 22 was 66% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 23 3.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-1-8) 1) 1.25 g, photoacid generator (F-2) 0.05 g, pigment dispersion (X-1-1) 2.1 g mixed with solvent (E-2) 22.20 g, solvent (E -1) Ink 23 was prepared by adding 7.31 g and stirring. The silver fine particle content based on the total solid content of the ink 23 was 78% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 24 For 59.33 g of silver fine particle dispersion (A-1-9), 4.22 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H— 1) To a mixture of 0.30 g and 8.41 g of pigment dispersion (X-1-2), 4.10 g of solvent (E-2) and 23.25 g of solvent (E-1) were added and stirred. Ink 24 was produced. The silver fine particle content based on the total solid content of the ink 24 was 69% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 25 4.63 g of 40% by mass alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver fine particle dispersion (A-2-2) 1) 1.30 g, photoacid generator (F-1) 0.05 g, sensitizer (G-1) 0.001 g mixed with solvent (E-2) 23.25 g, solvent (E-1 Ink 25 was prepared by adding and stirring 7.31 g. The silver fine particle content relative to the total solid content of the ink 25 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 26 6.59 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 55.47 g of silver fine particle dispersion (A-2-3) 1) To a mixture of 1.98 g and dye solution (X-2-1) 4.0 g, 8.30 g of solvent (E-2) and 23.25 g of solvent (E-1) were added and stirred. Ink 26 was produced. The silver fine particle content based on the total solid content of the ink 26 was 67% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 27 2.68 g of 40% by mass alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 68.00 g of silver fine particle dispersion (A-4-2) 1) To the mixture of 0.47 g, 4.89 g of solvent (E-2) and 23.25 g of solvent (E-1) were added and stirred to prepare ink 27. The silver fine particle content based on the total solid content of the ink 27 was 87% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 28 10.51 g of 40% by weight alkali-soluble resin (B-1), 0.49 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 51.75 g of silver fine particle dispersion (A-4-3) 1) To a mixture of 2.37 g and photoacid generator (F-1) 0.05 g, 23.25 g of solvent (E-2) and 11.92 g of solvent (E-1) were added and stirred. Ink 28 was produced. The silver fine particle content based on the total solid content of the ink 28 was 66% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 29 4.63 g of 40% by mass alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H—) with respect to 63.28 g of silver particle dispersion (A-5-2) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 29.
- the silver particle content with respect to the total solid content of the ink 29 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Example 30 For 59.33 g of the silver fine particle dispersion (A-5-3), 3.42 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H— 1) To a mixture of 0.30 g and 10.0 g of dye solution (X-2-2), 8.30 g of solvent (E-2) and 23.25 g of solvent (E-1) were added and stirred. Ink 30 was produced. The silver fine particle content based on the total solid content of the ink 30 was 68% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Comparative Example 1 4.63 g of 40% by weight alkali-soluble resin (B-1), 0.41 g of photopolymerization initiator (D-1), acrylic monomer (H--) with respect to 63.28 g of silver fine particle dispersion (A-6-1) 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 31.
- the silver fine particle content with respect to the total solid content of the ink 31 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Comparative Example 2 40.3% by weight alkali-soluble resin (B-7) 4.40 g, photopolymerization initiator (D-1) 0.41 g, acrylic monomer (H— 1) 23.25 g of solvent (E-2) and 7.31 g of solvent (E-1) were added to a mixture of 1.30 g and stirred to prepare ink 32.
- the silver fine particle content based on the total solid content of the ink 32 was 80% by mass. Patterning property and volume resistance were evaluated in the same manner as in Example 1.
- Tables 4 to 7 show the evaluation results of Examples 2 to 30 and Comparative Examples 1 and 2.
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Abstract
Description
(A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子における導電性微粒子としては、例えば、金(Au)、銀(Ag)、銅(Cu)、ニッケル(Ni)、錫(Sn)、ビスマス(Bi)、鉛(Pb)、亜鉛(Zn)、パラジウム(Pd)、白金(Pt)、アルミニウム(Al)、タングステン(W)またはモリブデン(Mo)等の金属微粒子が挙げられるが、金、銀、銅、ニッケル、錫、ビスマス、鉛、亜鉛、パラジウム、白金、アルミニウムおよび炭素からなる群から選ばれる少なくとも一つの元素を含有する金属微粒子であることが好ましく、銀の金属微粒子であることがより好ましい。
Dp=6/(ρSw)
粉体の比表面積Sw(m2/g)(BET値)は、全自動比表面積測定装置(例えば、MacsorbHMmodel-1201;Mountech株式会社製)で測定することができる。
(A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子における導電性微粒子は、炭素単体物および/または炭素化合物により表面が被覆されている。炭素単体物および/または炭素化合物からなる、導電性微粒子の表面を被覆する層(以下、「表面被覆層」)が存在することにより、導電性微粒子同士の融着を抑制することができる。
W2=π/6×Dp3ρ×n
そして、以下の式から表面被覆層の平均厚みAを算出することができる。
W1-W2={4/3×π(Dp/2+A)3-π/6×Dp3}×2.0×n
感光性樹脂組成物中の(A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子の含有量としては、残留有機成分が導電性微粒子同士の接触を妨げず、所望の導電性が得られ、より高解像度のパターン加工性を得るために、組成物中の全固形分に対し、70~95質量%であることが好ましく、75~95質量%であることがより好ましく、75~90質量%であることがさらに好ましい。その範囲内で含有することで、室温における長期保管にも優れ、容易にパターン加工性を発現できるだけでなく、100~300℃で、空気下で熱処理することによって、表面被覆層である炭素単体物および/または炭素化合物が、空気中の酸素によって一部または全部分解し、全固形分中の導電性物質濃度を上昇させて導電性を発現させることができる。ここで全固形分とは、感光性樹脂組成物が含有する成分の内、溶剤を除く全成分をいう。
(B)酸解離性基を有するアルカリ可溶性樹脂は、一般的に、カルボキシル基を含有する化合物と酸解離性基を有する化合物とを共重合することにより得られる。より具体的な例としては、カルボキシル基を含有する(メタ)アクリル酸化合物と、酸解離性基を有する(メタ)アクリル酸エステルとの共重合が挙げられる。この場合には、酸解離性基を有するアクリル樹脂が得られる。このアクリル樹脂は側鎖にカルボキシル基を有するため、アルカリ可溶性である。
ラジカル重合性基を導入するためには、カルボキシル基を有する樹脂と、ラジカル重合性基を有する一置換エポキシ化合物とを反応させることが好ましい。この場合、カルボキシル基を有する樹脂におけるカルボキシル基の一部と、ラジカル重合性基を有する一置換エポキシ化合物におけるエポキシ基を反応させることが好ましい。カルボキシル基を有する樹脂としては、カルボキシル基を有するアクリル樹脂が好ましい。ラジカル重合性基を含有することで、光ラジカル重合が可能となる。ラジカル重合性基は、光ラジカル重合反応性が高い、(メタ)アクリロイル基が好ましい。
本発明の感光性樹脂組成物は、(C)分散剤を含有しても構わない。(C)分散剤を含有することで、感光性樹脂組成物中に(A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子を安定的に存在させることができる。
本発明の感光性樹脂組成物は、(D)光重合開始剤を含有しても構わない。(D)光重合開始剤を含有することで、感光性樹脂組成物にネガ型感光性を付与することができる。
本発明の感光性樹脂組成物は、(E)溶剤を含有しても構わない。
本発明の感光性樹脂組成物は、分散性向上や、導電性コントロールのため、(A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子以外の他の粒子を含有しても構わない。他の粒子としては、例えば、表面被覆されていない金属微粒子若しくは金属酸化物微粒子、有機顔料または無機顔料が挙げられる。
本発明の感光性樹脂組成物は、(F)光酸発生剤および/または熱酸発生剤を含有しても構わない。発生した酸によって、(B)酸解離性基を有するアルカリ可溶性樹脂中の酸解離性基の分解が促進され、空気下での熱処理温度を低下させることが可能となる。
本発明の感光性樹脂組成物が(F)光酸発生剤を含有する場合、感光性樹脂組成物はさらに増感剤を含有しても構わない。増感剤は、熱処理により気化するもの、または、硬化膜に残存した場合においても、光照射によって退色するものが好ましく、パターン加工における高解像性の観点から、光照射によって退色するものがより好ましい。
R1~R8におけるアルキル基としては、例えば、メチル基、エチル基またはn-プロピル基が挙げられる。アルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基またはペンチルオキシ基が挙げられる。アルケニル基としては、例えば、ビニル基、アクリロキシプロピル基またはメタクリロキシプロピル基が挙げられる。アリール基としては、例えば、フェニル基、トリル基またはナフチル基が挙げられる。アシル基のとしては、例えば、アセチル基が挙げられる。なお、化合物の気化性および光二量化の反応性の観点から、R1~R8は水素または炭素数は1~6の有機基であることが好ましく、R1、R4、R5およびR8は水素であることがより好ましい。
本発明の感光性樹脂組成物は、(X)可視光に吸収を有する顔料および/または染料を、導電性微粒子同士の接触および融着を阻害しない範囲で含有しても構わない。感光性樹脂組成物がX)可視光に吸収を有する顔料および/または染料を含有することより、ポストベーク後の導電性パターンの可視光反射を抑制できる。
本発明の感光性樹脂組成物は、感光性能を調整し、パターン加工性を向上する観点から、アクリルモノマーまたは酸解離性基を有さないその他のアクリル系ポリマーを、導電性微粒子同士の接触および融着を阻害しない範囲内で含有しても構わない。
本発明の感光性樹脂組成物は、分散機を用いて樹脂溶液中に直接、導電性微粒子を分散させて製造しても構わないが、導電性微粒子を均一に分散することは困難であるため、分散剤を用いて、予め有機溶剤中に導電性微粒子を分散させた分散液を調製し、この分散液を、モノマー、ポリマー、密着改良剤、界面活性剤および重合禁止剤等を含有する溶液と混合する方法により製造することが好ましい。表面被覆された銀微粒子の分散液は、表面被覆層が損傷を受けるのを防ぐために、マイルド分散機またはメディアレス分散機を用いて分散させることが好ましく、メディアレス分散機を用いて分散させることがより好ましい。表面被覆された銀微粒子の分散液は、例えば、マイルド分散機ナノゲッターまたは高圧湿式メディアレス微粒化装置ナノマイザー)等の分散機を用いて、有機溶剤中に銀微粒子を分散させて製造することができる。ボールミル、サンドグラインダー、3本ロールミルまたは高速度衝撃ミル等の分散方法は、銀微粒子の表面被覆層が損傷され、銀微粒子同士の融着を促進してしまう場合がある。
次に、本発明の感光性樹脂組成物を用いた、フォトリソ法による導電性パターンの製造方法について説明する。
(A-1)表面炭素被覆層の平均厚みが1nmで粒子径が40nmの銀微粒子(日清エンジニアリング株式会社製)
(A-2)表面炭素被覆層の平均厚みが3nmで粒子径が60nmの銀微粒子(日清エンジニアリング株式会社製)
(A-3)表面炭素被覆層の平均厚みが10nmで粒子径が100nmの銀微粒子(日清エンジニアリング株式会社製)
(A-4)表面炭素被覆層の平均厚みが0.5nmで粒子径が50nmの銀微粒子(日清エンジニアリング株式会社製)
(A-5)表面炭素被覆層の平均厚みが0.2nmで粒子径が40nmの銀微粒子(日清エンジニアリング株式会社製)
(A-6)銀微粒子NB-01(Lot.2011-10;NaBond社製)
(A-7)表面炭素被覆層の平均厚みが30nmで粒子径が80nmの銀微粒子(日清エンジニアリング株式会社製)
(C)分散剤
(C-1)DISPERBYK140(ビックケミー・ジャパン株式会社製)(アミン価:146mgKOH/g)
(C-2)DISPERBYK21116(ビックケミー・ジャパン株式会社製)(アミン価:73mgKOH/g)。
(E-1)PGMEA:プロピレングリコールモノメチルエーテルアセテート
(E-2)DAA:ジアセトンアルコール
導電性微粒子分散体の作製
銀微粒子分散体(A-1-1)の作製
銀微粒子(A-1)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.14gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-1)を得た。
銀微粒子(A-1)75.00g、分散剤(C-1)3.82g、溶剤(E-1)183.91gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-2)を得た。
銀微粒子(A-1)85.00g、分散剤(C-1)4.3g、溶剤(E-1)208.4gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-3)を得た。
銀微粒子(A-1)70.00g、分散剤(C-1)3.34g、溶剤(E-1)171.13gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-4)を得た。
銀微粒子(A-1)88.00g、分散剤(C-1)2.61g、溶剤(E-1)211.42gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-5)を得た。
銀微粒子(A-1)65.00g、分散剤(C-1)3.32g、溶剤(E-1)159.41gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-6)を得た。
銀微粒子(A-1)93.00g、分散剤(C-1)2.61g、溶剤(E-1)223.09gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、銀粒子分散体(A-1-7)を得た。
銀微粒子(A-2)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.14gに対し、上記銀微粒子分散体(A-1-1)と同様にして銀微粒子分散体(A-2-1)を作製した。
銀微粒子(A-3)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.14gに対し、上記銀微粒子分散体(A-1-1)と同様にして銀微粒子分散体(A-3-1)を作製した。
銀微粒子(A-4)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.1gに対し、上記銀微粒子分散体(A-1-1)と同様にして銀微粒子分散体(A-4-1)を作製した。
銀微粒子(A-5)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.1gに対し、上記銀粒子分散体(A-1-1)と同様にして銀微粒子分散体(A-5-1)を作製した。
銀微粒子(A-6)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.1gに対し、上記銀粒子分散体(A-1-1)と同様にして銀微粒子分散体(A-6-1)を作製した。
銀微粒子(A-7)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.1gに対し、上記銀粒子分散体(A-1-1)と同様にして銀微粒子分散体(A-7-1)を作製した。
銀微粒子(A-1)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.14gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、マイルド分散機ナノゲッター(アシザワファインテック(株))を用いて分散し、銀粒子分散体(A-1-8)を得た。
銀微粒子(A-1)75.00g、分散剤(C-1)3.82g、溶剤(E-2)183.91gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、高圧湿式メディアレス微粒化装置ナノマイザー(ナノマーザー(株))を用いて分散し、銀粒子分散体(A-1-9)を得た。
銀微粒子(A-2)80.00g、分散剤(C-2)4.06g、溶剤(E-1)196.14gに対し、上記銀微粒子分散体(A-1-8)と同様にして銀微粒子分散体(A-2-2)を作製した。
銀微粒子(A-2)70g、分散剤(C-2)3.34g、溶剤(E-2)171.13gに対し、上記銀微粒子分散体(A-1-9)と同様にして銀微粒子分散体(A-2-3)を作製した。
銀微粒子(A-4)88.00g、分散剤(C-2)2.61g、溶剤(E-2)211.42gに対し、上記銀微粒子分散体(A-1-8)と同様にして銀微粒子分散体(A-4-2)を作製した。
銀微粒子(A-4)65.00g、分散剤(C-1)3.32g、溶剤(E-1)159.41gに対し、上記銀微粒子分散体(A-1-9)と同様にして銀微粒子分散体(A-4-3)を作製した。
銀微粒子(A-5)80.00g、分散剤(C-1)4.06g、溶剤(E-1)196.14gに対し、上記銀微粒子分散体(A-1-8)と同様にして銀微粒子分散体(A-5-2)を作製した。
銀微粒子(A-5)75.00g、分散剤(C-1)3.82g、溶剤(E-2)183.91gに対し、上記銀微粒子分散体(A-1-9)と同様にして銀微粒子分散体(A-5-3)を作製した。
酸解離性基含有アルカリ可溶性樹脂溶液(B-1)の合成
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEA(プロピレングリコールメチルエーテルアセテート)を50g仕込んだ。その後、メタクリル酸を23.26g、ベンジルメタクリレートを31.46g、ジシクロペンタニルメタクリレートを32.80g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを12.69g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-1)を得た。得られたアクリル樹脂溶液(B-1)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-1)の重量平均分子量は24,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEA(プロピレングリコールメチルエーテルアセテート)を50g仕込んだ。その後、メタクリル酸を21.92g、ベンジルメタクリレートを29.90g、ジシクロペンタニルメタクリレートを31.18g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にアクリル酸4‐(グリシジルオキシ)ブチルを17.00g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-2)を得た。得られたアクリル樹脂溶液(B-2)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-2)の重量平均分子量は23,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEA(プロピレングリコールメチルエーテルアセテート)を50g仕込んだ。その後、メタクリル酸を15.69g、ベンジルメタクリレートを69.12g、ジシクロペンタニルメタクリレートを48.65g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを10.46g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-3)を得た。得られたアクリル樹脂溶液(B-3)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-3)の重量平均分子量は22,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEA(プロピレングリコールメチルエーテルアセテート)を50g仕込んだ。その後、メタクリル酸を6.68g、ベンジルメタクリレートを109.65g、ジシクロペンタニルメタクリレートを17.1g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを5.51g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-4)を得た。得られたアクリル樹脂溶液(B-4)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-4)の重量平均分子量は22,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEAを50g仕込んだ。その後、メタクリル酸を15.69g、ベンジルメタクリレートを9.16g、ジシクロペンタニルメタクリレートを48.65g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを10.46g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-5)を得た。得られたアクリル樹脂溶液(B-5)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-5)の重量平均分子量は25,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEA(プロピレングリコールメチルエーテルアセテート)を50g仕込んだ。その後、メタクリル酸を23.26g、tert-ブチルメタクリレートを25.6g、ジシクロペンタニルメタクリレートを32.80g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを12.69g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-6)を得た。得られたアクリル樹脂溶液(B-6)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-6)の重量平均分子量は24,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEAを50g仕込んだ。その後、メタクリル酸を15.69g、スチレンを37.45g、ジシクロペンタニルメタクリレートを46.86g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを10.46g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-7)を得た。得られたアクリル樹脂溶液(B-7)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-7)の重量平均分子量は25,000であった。
500mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEAを50g仕込んだ。その後、メタクリル酸を15.69g、ベンジルメタクリレートを3.88g、ジシクロペンタニルメタクリレートを48.65g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを10.46g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-8)を得た。得られたアクリル樹脂溶液(B-8)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-8)の重量平均分子量は25,000であった。
1000mLのフラスコに2,2’-アゾビス(イソブチロニトリル)を2g、PGMEA(プロピレングリコールメチルエーテルアセテート)を100g仕込んだ。その後、メタクリル酸を6.68g、ベンジルメタクリレートを214.02g、ジシクロペンタニルメタクリレートを17.1g仕込み、室温でしばらく撹拌し、フラスコ内をバブリングによって十分に窒素置換した後、70℃で5時間加熱撹拌した。次に、得られた溶液にメタクリル酸グリシジルを5.51g、ジメチルベンジルアミンを1g、p-メトキシフェノールを0.2g、PGMEAを100g添加し、90℃で4時間加熱撹拌し、アクリル樹脂溶液(B-9)を得た。得られたアクリル樹脂溶液(B-9)に固形分濃度が40質量%になるようにPGMEAを加えた。アクリル樹脂(B-9)の重量平均分子量は22,000であった。
(D-1)イルガキュアOXE02(オキシムエステル系化合物;BASF社製)
(F)光酸発生剤および/または熱酸発生剤
(F-1)トリフェニルスルホニウムトリフルオロメタンスルホネート(オニウム塩系光酸発生剤;東京化成工業社製;)
(F-2)SI-100(熱酸発生剤;三新化学工業製)。
(G-1)9,10-ジエトキシアントラセン、9,10-ジプロポキシアントラセン(DPA;川崎化成工業社製)
(H)アクリルモノマー
(H-1)ライトアクリレートPE-4A(共栄社化学社製)
(X)可視光に吸収を有する顔料および/または染料
(X-1-1)顔料分散体
PG58(“ファストーゲン”(登録商標)グリーン A110;DIC社製)80g、分散剤(C-1)4.06g、溶剤(E-2)84.06gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、固形分50質量%(顔料濃度47.59質量%)の緑色分散体(X-1-1)を得た。
(X-1-2)顔料分散体
カーボンブラックMA100(粒子径:24nm、三菱化学社製)80g、分散剤(C-2)4.06g、溶剤(E-2)84.06gに対し、ホモジナイザーにて、1200rpm、30分の混合処理を施し、さらに、その混合液を、ジルコニアビーズが充填されたミル型分散機を用いて分散し、固形分50質量%(顔料濃度47.59質量%)の黒色分散体(X-1-2)を得た。
Plast Blue8540(FS Blue1502;有本化学工業社製)84.06gと、溶剤(E-2)84.06gとを、ホモジナイザーにて、1200rpm、30分の混合処理を施して溶解させ、固形分50質量%の青色染料溶液(X-2-1)を得た。
NUBIAN Black PA-2802(オリヱント化学工業社製)84.06gと、溶剤(E-2)84.06gとを、ホモジナイザーにて、1200rpm、30分の混合処理を施して溶解させ、固形分50質量%の黒色染料溶液(X-2-2)を得た。
パターニング性評価の方法について、実施例1を例に挙げて説明する。まず銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-2)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク1を作製した。
上記パターニング性評価に用いたものと同じインクを無アルカリガラス基板上にスピンコーター(1H-360S;ミカサ(株)製)を用いて500rpmで10秒回転した後、1000rpmで4秒回転してスピンコートした後、ホットプレートを用いて90℃で2分間プリベークし、膜厚1μmのプリベーク膜を作製した。得られたプリベーク膜に、PLAを用いて超高圧水銀灯を光源として、長方形の透光パターン(10mm×15mm)を有するフォトマスクを介して100μmのギャップで露光した。その後、自動現像装置を用いて、0.045質量%水酸化カリウム水溶液で90秒間シャワー現像し、次いで水で30秒間リンスした。その後、オーブン(「IHPS-222」;エスペック(株)製)を用いて以下の三条件でポストベークを施すことで体積抵抗評価パターンを得た。
(1)空気中 230℃ 30分
(2)空気中 250℃ 30分
(3)空気中 280℃ 30分
上記のように加工された長方形パターンに対し、表面抵抗測定機(ロレスタ-FP;三菱油化株式会社製)で測定した表面抵抗値ρs(Ω/□)と、表面粗さ形状測定機(サーフコム1400D;株式会社東京精密製)にて測定した膜厚t(cm)とを乗算することで、体積抵抗値(μΩ・cm)を算出した。
上記の体積抵抗評価方法で作製した基板の内、空気中、230℃、30分ポストベークを施した基板の長方形パターンに対して、分光測色計(CM-2600d;コニカミノルタ社製)のSCIモードで、450nmにおける反射率を測定した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク1を作製した。インク1の全固形分に対する銀微粒子含有量は80質量%であった。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-2)4.40g、光重合開始剤(D-2)0.41g、アクリルモノマー(H-2)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク2を作製した。インク2の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-3)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク3を作製した。インク3の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-4)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク4を作製した。インク4の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-5)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク5を作製した。インク5の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-6)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク6を作製した。インク6の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-2-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク7を作製した。インク7の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-3-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク8を作製した。インク8の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀粒子分散体(A-4-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク9を作製した。インク9の全固形分に対する銀粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀粒子分散体(A-5-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク10を作製した。インク10の全固形分に対する銀粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、光酸発生剤(F-1)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク11を作製した。インク11の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、光酸発生剤(F-2)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク12を作製した。インク12の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、光酸発生剤(F-1)0.05g、増感剤(G-1)0.001gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク13を作製した。インク13の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-2)59.33gに対し、40質量%アルカリ可溶性樹脂(B-1)7.37g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、光酸発生剤(F-1)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)8.3gを添加し撹拌することにより、インク14を作製した。インク14の全固形分に対する銀微粒子含有量は75質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-3)67.07gに対し、40質量%アルカリ可溶性樹脂(B-1)3.27g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)0.62g、光酸発生剤(F-1)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)5.34gを添加し撹拌することにより、インク15を作製した。インク15の全固形分に対する銀微粒子含有量は85質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-4)55.47gに対し、40質量%アルカリ可溶性樹脂(B-1)8.54g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.98g、光酸発生剤(F-1)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)10.30gを添加し撹拌することにより、インク16を作製した。インク16の全固形分に対する銀微粒子含有量は71質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-5)68.00gに対し、40質量%アルカリ可溶性樹脂(B-1)2.92g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)0.47g、光酸発生剤(F-1)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)4.89gを添加し撹拌することにより、インク17を作製した。インク17の全固形分に対する銀微粒子含有量は88質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-7)71.65gに対し、40質量%アルカリ可溶性樹脂(B-1)1.37g、光重合開始剤(D-1)0.49g、アクリルモノマー(H-1)0.22g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)3.28gを添加し撹拌することにより、インク18を作製した。インク18の全固形分に対する銀微粒子含有量は92質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-7-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク19を作製した。インク19の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-8)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク20を作製した。インク20の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-9)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク21を作製した。インク21の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-6)51.75gに対し、40質量%アルカリ可溶性樹脂(B-1)10.18g、光重合開始剤(D-1)0.49g、アクリルモノマー(H-1)2.37g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)11.92gを添加し撹拌することにより、インク22を作製した。インク22の全固形分に対する銀微粒子含有量は66質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-8)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)3.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.25g、光酸発生剤(F-2)0.05g、顔料分散体(X-1-1)2.1gを混合したものに溶剤(E-2)22.20g、溶剤(E-1)7.31gを添加し撹拌することにより、インク23を作製した。インク23の全固形分に対する銀微粒子含有量は78質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-9)59.33gに対し、40質量%アルカリ可溶性樹脂(B-1)4.22g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)0.30g、顔料分散体(X-1-2)8.41gを混合したものに溶剤(E-2)4.10g、溶剤(E-1)23.25gを添加し撹拌することにより、インク24を作製した。インク24の全固形分に対する銀微粒子含有量は69質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-2-2)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、光酸発生剤(F-1)0.05g、増感剤(G-1)0.001gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク25を作製した。インク25の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-2-3)55.47gに対し、40質量%アルカリ可溶性樹脂(B-1)6.59g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.98g、染料溶液(X-2-1)4.0gを混合したものに溶剤(E-2)8.30g、溶剤(E-1)23.25gを添加し撹拌することにより、インク26を作製した。インク26の全固形分に対する銀微粒子含有量は67質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-4-2)68.00gに対し、40質量%アルカリ可溶性樹脂(B-1)2.97g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)0.47gを混合したものに溶剤(E-2)4.89g、溶剤(E-1)23.25gを添加し撹拌することにより、インク27を作製した。インク27の全固形分に対する銀微粒子含有量は87質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-4-3)51.75gに対し、40質量%アルカリ可溶性樹脂(B-1)10.18g、光重合開始剤(D-1)0.49g、アクリルモノマー(H-1)2.37g、光酸発生剤(F-1)0.05gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)11.92gを添加し撹拌することにより、インク28を作製した。インク28の全固形分に対する銀微粒子含有量は66質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀粒子分散体(A-5-2)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30gを混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク29を作製した。インク29の全固形分に対する銀粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-5-3)59.33gに対し、40質量%アルカリ可溶性樹脂(B-1)3.42g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)0.30g、染料溶液(X-2-2)10.0gを混合したものに溶剤(E-2)8.30g、溶剤(E-1)23.25gを添加し撹拌することにより、インク30を作製した。インク30の全固形分に対する銀微粒子含有量は68質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-6-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-1)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク31を作製した。インク31の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
銀微粒子分散体(A-1-1)63.28gに対し、40質量%アルカリ可溶性樹脂(B-7)4.40g、光重合開始剤(D-1)0.41g、アクリルモノマー(H-1)1.30g、を混合したものに溶剤(E-2)23.25g、溶剤(E-1)7.31gを添加し撹拌することにより、インク32を作製した。インク32の全固形分に対する銀微粒子含有量は80質量%であった。実施例1と同様にパターニング性と体積抵抗を評価した。
Claims (17)
- (A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子、(B)酸解離性基を有するアルカリ可溶性樹脂を含有する、感光性樹脂組成物。
- 前記(B)酸解離性基を有するアルカリ可溶性樹脂が、さらにラジカル重合性基を有する、請求項1記載の感光性樹脂組成物。
- 前記ラジカル重合性基として、(メタ)アクリロイル基を有する、請求項2記載の感光性樹脂組成物。
- 前記酸解離性基が、炭素数4~15の有機基である、請求項1~3のいずれか一項記載の感光性樹脂組成物。
- さらに(F)光酸発生剤および/または熱酸発生剤を含有する、請求項1~4のいずれか一項記載の感光性樹脂組成物。
- さらに(X)可視光領域に吸収を有する顔料および/または染料を含有する、請求項1~5のいずれか一項記載の感光性樹脂組成物。
- 前記(B)酸解離性基を有するアルカリ可溶性樹脂として、酸解離性基を有する化合物を20~80モル%ラジカル共重合したアルカリ可溶性樹脂を含有する、請求項1~6のいずれか一項記載の感光性樹脂組成物。
- 前記導電性微粒子が、銀微粒子である、請求項1~7のいずれか一項記載の感光性樹脂組成物。
- 前記導電性微粒子の粒子径が、10~100nmである、請求項1~8のいずれか一項記載の感光性樹脂組成物。
- 前記(A)炭素単体物および/または炭素化合物で表面被覆した導電性微粒子の表面被覆層の平均厚みが、0.1~10nmである、請求項1~9のいずれか一項記載の感光性樹脂組成物。
- 前記(A)炭素単体物および/または炭素化合物で表面被覆された導電性微粒子を、全固形分に対し70~95質量%の範囲内で含有する、請求項1~10のいずれか一項記載の感光性樹脂組成物。
- 請求項1~11のいずれか一項記載の感光性樹脂組成物を基板面上に塗布する工程、それを乾燥する工程、それを露光および現像してパターンを形成する工程、および、それをポストベークする工程を備える、導電性パターンの製造方法。
- 請求項12記載の導電性パターンを具備する、基板。
- 前記導電性パターンの幅が、5μm以下である、請求項13記載の基板。
- 請求項13または14記載の基板を具備する、素子。
- 請求項13または14記載の基板を具備する、タッチパネル。
- 請求項13または14記載の基板を具備する、イメージセンサ。
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US10001704B2 (en) | 2018-06-19 |
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EP3133443A1 (en) | 2017-02-22 |
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KR102074712B1 (ko) | 2020-03-17 |
CN106462058A (zh) | 2017-02-22 |
JPWO2015159655A1 (ja) | 2017-04-13 |
TW201543155A (zh) | 2015-11-16 |
EP3133443A4 (en) | 2018-01-10 |
US20170038682A1 (en) | 2017-02-09 |
CN106462058B (zh) | 2019-08-13 |
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