WO2014077136A1 - 感光性導電ペースト、積層基板、導電パターンの製造方法及び静電容量型タッチパネル - Google Patents
感光性導電ペースト、積層基板、導電パターンの製造方法及び静電容量型タッチパネル Download PDFInfo
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- WO2014077136A1 WO2014077136A1 PCT/JP2013/079622 JP2013079622W WO2014077136A1 WO 2014077136 A1 WO2014077136 A1 WO 2014077136A1 JP 2013079622 W JP2013079622 W JP 2013079622W WO 2014077136 A1 WO2014077136 A1 WO 2014077136A1
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- conductive paste
- photosensitive
- pattern
- substrate
- oxide
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Classifications
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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
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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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
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/05—Patterning and lithography; Masks; Details of resist
- H05K2203/0502—Patterning and lithography
- H05K2203/0514—Photodevelopable thick film, e.g. conductive or insulating paste
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4664—Adding a circuit layer by thick film methods, e.g. printing techniques or by other techniques for making conductive patterns by using pastes, inks or powders
Definitions
- the present invention relates to a photosensitive conductive paste, a laminated substrate, a method for manufacturing a conductive pattern, and a capacitive touch panel.
- Patent Document 3 an electrically conductive paste that can be etched
- Patent Document 4 A photosensitive paste for forming a conductive pattern capable of forming a low-rate organic-inorganic composite conductive pattern has also been developed (Patent Document 4).
- the present invention forms a conductive pattern with a low specific resistivity that is capable of fine patterning and low-temperature conductivity without adversely affecting the material such as the substrate, and has excellent adhesion to the substrate.
- An object is to provide a photosensitive conductive paste and a method for producing a conductive pattern using the same.
- the present invention provides a photosensitive conductive paste, a laminated substrate, and a method for producing a conductive pattern described in the following (1) to (5).
- a photosensitive conductive paste comprising an ion adsorbent D selected from the group consisting of silicon, zeolite, and carbon-based powder.
- a laminated substrate comprising a conductive layer formed from the photosensitive conductive paste according to (1) or (2).
- a capacitive touch panel comprising a conductive pattern formed from the photosensitive conductive paste according to (1) or (2) as a peripheral wiring, and the peripheral wiring having a pitch of 100 ⁇ m or less.
- the photosensitive conductive paste of the present invention fine patterning and low-temperature conductivity can be achieved without adversely affecting the material such as the substrate.
- a conductive pattern having excellent adhesion to the substrate and a low specific resistivity can be formed.
- the photosensitive conductive paste of the present invention comprises conductive particles A, photosensitive organic compound B, epoxy resin C, magnesium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, zirconium oxide, magnesium silicate. And an ion adsorbent D selected from the group consisting of silicon dioxide, zeolite, and carbon-based powder.
- the paste is applied on a substrate, dried to remove the solvent, and then a desired function can be obtained by heating.
- the method for producing a conductive pattern of the present invention comprises a coating step of applying the photosensitive conductive paste of the present invention on a substrate to obtain a coating film, a drying step of drying the coating film, and the drying step described above.
- the conductive pattern obtained by the method for producing a conductive pattern of the present invention exhibits conductivity when the conductive particles A contained in the photosensitive conductive paste of the present invention are brought into contact with each other by curing shrinkage during heating. It is.
- Examples of the conductive particles A include Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, Sb, ruthenium oxide, Cr, Ti or indium particles, alloy particles of these metals, or these.
- a mixture of particles may be mentioned.
- Ag, Au or Pt particles which are noble metals from the viewpoint of conductivity, Cu are preferable, noble metal particles are more preferable from the viewpoint of stability, and Ag particles are more preferable from the viewpoint of cost.
- Cu is excellent in terms of cost, not only conductivity is lowered because part of the Cu is easily ionized, but addition of an ion adsorbent consumes Cu ions and adversely affects materials such as a substrate. May reduce the adsorption efficiency of other ions that affect
- the volume average particle diameter of the conductive particles A is preferably 0.5 to 10 ⁇ m, more preferably 1 to 6 ⁇ m.
- the volume average particle diameter is 1 ⁇ m or more, the contact probability between the conductive fillers in the heating step is improved, and the specific resistance and disconnection probability of the manufactured conductive pattern are lowered. Furthermore, in the exposure process, the exposure light can smoothly pass through the coating film obtained by applying the photosensitive conductive paste, facilitating fine patterning.
- the volume average particle diameter is 6 ⁇ m or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the manufactured conductive pattern are improved.
- the volume average particle diameter can be measured by a Coulter counter method.
- the amount of conductive particles A added is preferably 70 to 95% by weight, more preferably 80 to 90% by weight, based on the total solid content in the photosensitive conductive paste.
- the addition amount with respect to the total solid content is 80% by weight or more, the contact probability between the conductive particles A in the curing shrinkage in the heating step is improved, and the specific resistance and the disconnection probability of the manufactured conductive pattern are lowered.
- the addition amount with respect to the total solid content is 90% by weight or less, the exposure light can smoothly pass through the coating film obtained by applying the photosensitive conductive paste in the exposure process, and fine patterning is performed. Becomes easy.
- the total solid content means all components of the photosensitive conductive paste excluding the solvent.
- Photosensitive organic compound B refers to a monomer, oligomer or polymer having an unsaturated double bond in the molecule. More specifically, an acrylic copolymer is mentioned, for example.
- the acrylic copolymer refers to a copolymer containing an acrylic monomer having a carbon-carbon double bond as a copolymer component.
- Acrylic monomers include methyl acrylate, acrylic acid, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl acrylate, i-butyl acrylate, i-propane acrylate, glycidyl acrylate, N-methoxymethyl acrylamide, N-ethoxymethyl Acrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, 2-hydroxypropyl acrylate, Isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxy Ethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate,
- the photosensitive conductive paste of the present invention preferably contains a photopolymerization initiator.
- the photopolymerization initiator refers to a compound that is decomposed by ultraviolet rays or infrared rays to generate radicals or acids.
- photopolymerization initiator examples include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, Bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide, ethanone, 1- [9-ethyl-6-2 (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O -Acetyloxime), benzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4 '-Methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2'-diethoxyacetoph Non, 2,
- the addition amount of the photopolymerization initiator is preferably 0.05 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the photosensitive organic compound B and the epoxy resin C.
- the addition amount with respect to 100 parts by weight of the photosensitive organic compound B and the epoxy resin C is 5 parts by weight or more, the cured density of the exposed part of the photosensitive conductive paste increases, and the remaining film ratio after development increases.
- the addition amount with respect to 100 parts by weight of the photosensitive organic compound B and the epoxy resin C is 20 parts by weight or less, an excess of the photopolymerization initiator in the upper part of the coating film obtained by applying the photosensitive conductive paste. Light absorption is suppressed. As a result, a decrease in adhesion with the substrate due to the manufactured conductive pattern having an inversely tapered shape is suppressed.
- the photosensitive conductive paste of the present invention may contain a sensitizer together with a photopolymerization initiator.
- sensitizer examples include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2 , 6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone P-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole,
- the addition amount of the sensitizer is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the photosensitive organic compound B.
- the photosensitivity is sufficiently improved.
- the added amount with respect to 100 parts by weight of the photosensitive organic compound B is 10 parts by weight or less, excessive photoabsorption of the photopolymerization initiator particularly in the upper part of the coating film obtained by applying the photosensitive conductive paste. It is suppressed. As a result, a decrease in adhesion with the substrate due to the manufactured conductive pattern having an inversely tapered shape is suppressed.
- the epoxy resin C examples include a glycidyl group-containing compound which is a compound derived from epichlorohydrin or an unsaturated double bond adduct thereof. More specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, hydrogenated bisphenol type epoxy resin, Bisphenol fluorene type epoxy resin, biscresol fluorene type epoxy resin, bisphenoxyethanol fluorene type epoxy resin, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, trimethylol Propane polyglycidyl ether, resorcinol diglycidyl ether, neopen Diglycidyl ether,
- the addition amount of the epoxy resin C is preferably 0.05 to 30 parts by weight, more preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the photosensitive organic compound B.
- the added amount of the resin C containing an epoxy group with respect to 100 parts by weight of the photosensitive organic compound B is 0.05 parts by weight or more, the conductivity of the manufactured conductive pattern is increased.
- the pattern workability can be controlled when the amount added to 100 parts by weight of the photosensitive organic compound B is 30 parts by weight or less.
- the photosensitive conductive paste of the present invention contains an ion adsorbent D. Since the photosensitive electrically conductive paste of this invention uses the ion adsorbent D as an essential component, it can capture an excess ionic component and suppress the above-described adverse effects.
- the present inventors consider a specific ion adsorbent in consideration of adhesion to the substrate. Found to be selected.
- carbon-based powder examples include activated carbon, charcoal, acetylene black, ketjen black, carbon black, titanium black, carbon whisker or carbon nanotube, and graphite.
- an oxide zinc oxide, tin oxide, indium oxide, calcium oxide, magnesium oxide, zirconium oxide, magnetic iron oxide, ferrite, for example, alumina (aluminum oxide) represented by Al 2 O 3 xH 2 O
- alumina aluminum oxide represented by Al 2 O 3 xH 2 O
- examples thereof include silica (silicon dioxide), titanium oxide, barium titanate, lead zirconate titanate, potassium titanate, cerium oxide, and antimony oxide.
- These composite oxides and oxides may contain water.
- magnesium oxide, aluminum oxide, or silicon dioxide as a main component, a magnesium oxide-aluminum oxide composite oxide of 2.5 MgO ⁇ Al 2 O 3 ⁇ xH 2 O, Mg 0.7 ⁇ Al 0.3 O 1.15 , magnesium oxide-sodium oxide composite oxide Al 2 O 3 ⁇ Na 2 O ⁇ 2CO 3 ⁇ xH 2 O, magnesium oxide-silicon dioxide composite oxide 2MgO ⁇ 6SiO 2 ⁇ xH 2 O 2 or Al 2 O 3 ⁇ 9SiO 2 xH 2 O, which is a composite oxide of aluminum oxide and silicon dioxide, and aluminosilicate.
- natural zeolite commonly known as natural zeolite, synthetic zeolite, sodalite, natural mordenite, synthetic Examples thereof include zeolites such as mordenite.
- zeolites such as mordenite.
- Other examples include complex oxide-based minerals such as mica, synthetic mica, montmorillonite, vermiculite, talc, zonotolite, dosonite, sericite, glass flakes, and clay.
- borate salts boric acid, zinc borate, aluminum borate and the like can be mentioned.
- sulfates include barium sulfate, molybdenum disulfide, basic magnesium sulfate, and magnesium sulfate.
- zirconium phosphate etc. are mention
- examples of silicates include sepiolite, silica gel, wollastonite, silica balloon, glass balloon, shirasu balloon, magnesium silicate, calcium silicate, and hydroxides such as aluminum hydroxide and magnesium hydroxide.
- examples of carbonates include calcium carbonate, magnesium carbonate, aluminum carbonate, zinc carbonate, boehmite, lithium carbonate, Al (OH) 3 .NaHCO 3 and the like.
- magnesium and aluminum carbonate mineral Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O, Mg 4.5 Al 2 (OH) 13 CO 3 , Mg 4 Al 2 (OH) 12 CO 3 .3.5H 2 O, Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 5 Al 2 (OH) 14 CO 3 .4H 2 O, Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O, Mg 3 Al 2 (OH) 10 CO 3 .1.7H 2 O, Mg 3 ZnAl 2 (OH) 12 CO 3 .xH 2 O, or Mg 3 ZnAl 2 ( OH) 12 CO 3 and the like.
- the ion adsorbent D is hydrotalcite magnesium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, zirconium oxide, magnesium silicate, silicon dioxide, zeolite.
- the inventors have found that it is preferable to select from the group consisting of carbonaceous powders and carbonaceous powders. They can also be used as a mixture.
- the ion adsorbent D is more preferably selected from the group consisting of hydrotalcite, magnesium oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, and carbon-based powder, and is preferably hydrotalcite. Is more preferable.
- the shape of the ion adsorbent D may be any of granular (particulate), polyhedral, spherical, irregular, flat, or needle-shaped, but the particle size distribution is sharp, there are few aggregates, and it is spherical. Preferred for smooth transmission of exposure light.
- the volume average particle diameter of the ion adsorbent D is preferably 0.03 to 10 ⁇ m, and more preferably 0.1 to 6 ⁇ m.
- the volume average particle diameter is 0.03 ⁇ m or more, the dispersibility and dispersion stability in the photosensitive conductive paste are increased, and the surface area is increased, so that the ion adsorption effect with respect to the addition amount is enhanced.
- the volume average particle diameter is 10 ⁇ m or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the manufactured conductive pattern are improved.
- the volume average particle diameter can be measured by a Coulter counter method.
- the addition amount of the ion adsorbent D is 50% by weight or more with respect to the total solid content in the photosensitive conductive paste, it is difficult to obtain the desired effect of the photosensitive conductive paste of the present invention.
- the addition amount of the ion adsorbent D is preferably 0.1 to 20% by weight with respect to the total solid content.
- the addition amount with respect to the total solid content is 0.1% by weight or more, the ion adsorption ability is improved.
- the addition amount with respect to the total solid content is 20% by weight or less, the influence on the conductivity of the manufactured conductive pattern is small.
- the photosensitive conductive paste of the present invention may contain a solvent.
- the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl lactate, 1-methoxy-2-propanol. 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol or propylene glycol monomethyl ether acetate or a mixture of these solvents.
- the photosensitive conductive paste of the present invention may contain ionic components such as chlorine ions.
- ionic components such as chlorine ions.
- the conductivity of the obtained conductive film is improved.
- an excess ionic component when an excess ionic component is present, it may cause adverse effects such as reduced adhesion of the produced conductive pattern and deterioration of the substrate, but the photosensitive conductive paste of the present invention is an ion adsorbent. Since D is an essential constituent component, excess ionic components can be captured and the above-described adverse effects can be suppressed.
- the photosensitive conductive paste of the present invention may contain additives such as a resin, a plasticizer, a leveling agent, a surfactant, a silane coupling agent, an antifoaming agent, or a pigment.
- the resin examples include novolak resin, phenol resin, polyimide precursor, closed ring polyimide, melamine resin, polyvinyl chloride, and polyvinylidene chloride.
- plasticizer examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, and glycerin.
- leveling agent examples include a special vinyl polymer or a special acrylic polymer.
- silane coupling agent examples include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane. Methoxysilane is mentioned.
- the photosensitive conductive paste is produced, for example, using a dispersing machine or a kneader such as a three-roller, a ball mill or a planetary ball mill.
- the photosensitive conductive paste of the present invention is applied onto a substrate to obtain a coating film, and the obtained coating film is dried to volatilize the solvent. Thereafter, the dried coating film is exposed through a pattern forming mask, and the exposed coating film is developed to form a desired pattern on the substrate. And if an obtained pattern is heated, a conductive pattern will be obtained.
- Examples of the substrate include a silicon wafer, a ceramic substrate, and a resin substrate.
- Examples of the ceramic substrate include a glass substrate, an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate.
- Examples of the resin substrate include an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, and a polysulfone series. Examples include a resin substrate, a polyimide film, a polyester film, or an aramid film.
- Examples of the method for applying the photosensitive conductive paste on the substrate include spin coating using a spinner, spray coating, roll coating, screen printing, or coating using a blade coater, die coater, calendar coater, meniscus coater, or bar coater. Is mentioned.
- the film thickness of the obtained coating film may be appropriately determined according to the coating method or the total solid content concentration or viscosity of the photosensitive conductive paste, but the film thickness after drying is within the range of 0.1 to 50 ⁇ m. It is preferable to become.
- the film thickness can be measured using a stylus type step gauge such as “Surfcom” (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thickness at three random positions may be measured with a stylus-type step gauge (length measurement: 1 mm, scanning speed: 0.3 mm / sec), and the average value may be defined as the film thickness. it can.
- Examples of the method for drying the obtained coating film to volatilize and remove the solvent include heat drying or vacuum drying using an oven, a hot plate, infrared rays, or the like.
- the heat drying is preferably 50 to 180 ° C., and the heating time is preferably 1 minute to several hours.
- the dried coating film is exposed by a photolithography method.
- a light source for exposure i-line (365 nm), h-line (405 nm) or g-line (436 nm) of a mercury lamp is preferable.
- the desired pattern is obtained by developing the exposed coating film using a developer and dissolving and removing unexposed portions.
- the developer used for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, and dimethyl acetate.
- An aqueous solution of aminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine may be mentioned.
- aqueous solutions include N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N— Polar solvents such as dimethylacetamide, dimethylsulfoxide or ⁇ -butyrolactone, alcohols such as methanol or ethanol or isopropanol, milk Ethyl, esters such as propylene glycol monomethyl ether acetate, cyclopentanone, cyclohexanone, may be added to ketones or surfactant, such as isobutyl ketone or methyl isobutyl ketone.
- Examples of the developer for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoryl tri
- Examples thereof include polar solvents such as amides or mixed solvents of these polar solvents with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol or ethyl carbitol.
- a development method for example, a method of spraying a developer onto the coating film surface while the substrate is left standing or rotating, a method of immersing the substrate in the developer, or an ultrasonic wave while immersing the substrate in the developer The method of applying is mentioned.
- the pattern obtained by development may be rinsed with a rinse solution.
- a rinse solution examples include water or an aqueous solution in which an alcohol such as ethanol or isopropyl alcohol or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate is added to water.
- the heating temperature is preferably 100 to 300 ° C, more preferably 100 to 200 ° C.
- the volume shrinkage of the resin increases, the contact probability between the conductive powders A increases, and the specific resistivity decreases.
- the photosensitive conductive paste of the present invention can obtain high conductivity by heating at a relatively low temperature of 200 ° C. or lower, a conductive pattern can be formed on a material such as a substrate having low heat resistance. .
- the conductive pattern manufactured using the photosensitive conductive paste of the present invention is suitably used as a peripheral wiring for a touch panel.
- the touch panel system include a resistive film type, an optical type, an electromagnetic induction type, and a capacitance type.
- the capacitance type touch panel particularly requires fine wiring, the photosensitive conductive paste of the present invention. Is more preferably used.
- the touch panel provided with the conductive pattern of the present invention as its peripheral wiring and the peripheral wiring is 100 ⁇ m pitch (wiring width + inter-wiring width) or less, the frame width can be narrowed and the view area can be widened.
- Photosensitive organic compound B (Synthesis Example 1; photosensitive organic compound B-1) Copolymer of ethyl acrylate (EA) / 2-ethylhexyl methacrylate (2-EHMA) / styrene (St) / acrylic acid (AA) (copolymerization ratio: 20 parts by weight / 40 parts by weight / 20 parts by weight / 15 parts by weight) Part) was added with 5 parts by weight of glycidyl methacrylate (GMA). In a nitrogen atmosphere reaction vessel, 150 g of diethylene glycol monoethyl ether acetate was charged, and the temperature was raised to 80 ° C. using an oil bath.
- This consists of 20 g ethyl acrylate, 40 g 2-ethylhexyl methacrylate, 20 g styrene, 15 g acrylic acid, 0.8 g 2,2′-azobisisobutyronitrile and 10 g diethylene glycol monoethyl ether acetate.
- the mixture was added dropwise over 1 hour. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction.
- ethylene oxide modified bisphenol A diacrylate FA-324A was obtained from 20 g of ethyl acrylate, 15 g of acrylic acid, 0.8 g of 2,2′-azobisisobutyronitrile and 10 g of diethylene glycol monoethyl ether acetate. The resulting mixture was added dropwise over 1 hour. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to stop the polymerization reaction.
- the mixture was mixed with an orbital mixer (hybrid mixer) “Awatori Nertaro” (registered trademark) (ARE-310; manufactured by Sinky Corporation) to obtain a photosensitive resin solution.
- Ag particles and the ion adsorbent D-1 were mixed with the obtained photosensitive resin solution so as to have the weight% shown in Table 1, and kneaded using three rollers (EXAKT M-50; manufactured by EXAKT).
- EXAKT M-50 manufactured by EXAKT
- a photosensitive conductive paste was applied by screen printing on a PET film having a thickness of 50 ⁇ m, and the obtained coating film was dried in a drying oven at 100 ° C. for 10 minutes.
- a group of straight lines arranged in a constant line and space (hereinafter referred to as L / S), that is, a translucent pattern, is defined as one unit, and after drying through a photomask having nine types of units having different L / S values.
- the coating film was exposed and developed to obtain patterns having different L / S values. Thereafter, all of the obtained nine patterns were cured in a drying oven at 140 ° C. for 30 minutes to obtain conductive patterns having different L / S values.
- the L / S value of each unit included in the photomask is 500/500, 250/250, 100/100, 50/50, 40/40, 30/30, 25/25, 20/20, 17 / 17, 15/15, and 10/10 (representing line width ( ⁇ m) / interval ( ⁇ m), respectively).
- the obtained conductive pattern is observed with an optical microscope, a conductive pattern having no residue between the patterns and having no pattern peeling is confirmed, and the L / S value can be developed.
- the value was / S.
- the developable L / S value is 30/30, 25/25, 20/20, 17/17, 15/15 or 10/10, and the developable L / S value is 100.
- the exposure is performed using an exposure apparatus (PEM-6M; manufactured by Union Optics Co., Ltd.) for full line exposure with an exposure amount of 200 mJ / cm 2 (wavelength 365 nm conversion), and development is performed with a 0.25 wt% Na 2 CO 3 aqueous solution.
- the substrate was immersed for 30 seconds, and then rinsed with ultrapure water.
- the developable L / S value was 20/20 ⁇ m, which was judged as ⁇ , and it was confirmed that a good pattern was processed.
- a photosensitive conductive paste is applied on a PET film “ELECRYSTA” (registered trademark) V270L-TFS (manufactured by Nitto Denko Corporation) with ITO by a screen printing method so that the film thickness of the coating film after drying is 7 ⁇ m.
- the obtained coating film was dried in a drying oven at 90 ° C. for 10 minutes, and then the entire surface was exposed. The exposure conditions were the same as those for the above processability evaluation. Then, after heating in a drying oven at 140 ° C. for 1 hour, a cut was made with a cutter into a 1 mm width and 10 ⁇ 10 grid pattern.
- Cellophane tape (manufactured by Nichiban Co., Ltd.) was attached to and peeled off from the entire cross-cut portion of this sample, and the initial evaluation was performed by counting the number of remaining masses. Subsequently, the sample was put into a constant temperature and humidity chamber SH-661 (manufactured by ESPEC Corporation) at 85 ° C. and 85% RH for 240 hours, and a cellophane tape was attached to the entire cut-out part of the cutout of the sample. The remaining mass was counted and evaluated after the constant temperature and humidity chamber was added.
- SH-661 manufactured by ESPEC Corporation
- Example 2 A photosensitive conductive paste having the composition shown in Table 1 was produced in the same manner as in Example 1, and the evaluation results are also shown in Table 1.
- the photosensitive conductive paste of the present invention can be suitably used for manufacturing conductive patterns such as peripheral wiring for touch panels.
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Abstract
Description
(1) 導電性粒子Aと、感光性有機化合物Bと、エポキシ樹脂Cと、ハイドロタルサイト、酸化マグネシウム、酸化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、炭酸マグネシウム、酸化ジルコニウム、ケイ酸マグネシウム、二酸化ケイ素、ゼオライト及び炭素系粉末からなる群から選ばれるイオン吸着剤Dと、を含む、感光性導電ペースト。
(2) 上記導電性粒子Aは、貴金属粒子である、上記(1)に記載の感光性導電ペースト。
(3) 上記(1)又は(2)に記載の感光性導電ペーストから形成された導電層を具備する、積層基板。
(4) 上記(1)又は(2)に記載の感光性導電ペーストを基板上に塗布して塗布膜を得る、塗布工程と、上記塗布膜を乾燥する、乾燥工程と、乾燥後の上記塗布膜を露光する、露光工程と、露光後の上記塗布膜を現像して、パターンを得る、現像工程と、上記パターンを加熱して、導電パターンを得る、加熱工程と、を備える、導電パターンの製造方法。
(5) 上記(1)又は(2)に記載の感光性導電ペーストから形成された導電パターンを周囲配線として備え、該周囲配線が100μmピッチ以下である、静電容量型タッチパネル。
(合成例1;感光性有機化合物B-1)
エチルアクリレート(EA)/メタクリル酸2-エチルヘキシル(2-EHMA)/スチレン(St)/アクリル酸(AA)の共重合体(共重合比率:20重量部/40重量部/20重量部/15重量部)にグリシジルメタクリレート(GMA)を5重量部付加反応させたもの
窒素雰囲気の反応容器中に、150gのジエチレングリコールモノエチルエーテルアセテートを仕込み、オイルバスを用いて80℃まで昇温した。これに、20gのエチルアクリレート、40gのメタクリル酸2-エチルヘキシル、20gのスチレン、15gのアクリル酸、0.8gの2,2’-アゾビスイソブチロニトリル及び10gのジエチレングリコールモノエチルエーテルアセテートからなる混合物を、1時間かけて滴下した。滴下終了後、さらに6時間重合反応を行った。その後、1gのハイドロキノンモノメチルエーテルを添加して、重合反応を停止した。引き続き、5gのグリシジルメタクリレート、1gのトリエチルベンジルアンモニウムクロライド及びジ10gエチレングリコールモノエチルエーテルアセテートからなる混合物を、0.5時間かけて滴下した。滴下終了後、さらに2時間付加反応を行った。得られた反応溶液をメタノールで精製することで未反応不純物を除去し、さらに24時間真空乾燥することで、感光性有機化合物B-1を得た。
エチレンオキサイド変性ビスフェノールAジアクリレートFA-324A(日立化成工業株式会社製)/EA/AAの共重合体(共重合比率:50重量部/10重量部/15重量部)にグリシジルメタクリレート(GMA)を5重量部付加反応させたもの
窒素雰囲気の反応容器中に、150gのジエチレングリコールモノエチルエーテルアセテートを仕込み、オイルバスを用いて80℃まで昇温した。これに、50gのエチレンオキサイド変性ビスフェノールAジアクリレートFA-324Aを、20gのエチルアクリレート、15gのアクリル酸、0.8gの2,2’-アゾビスイソブチロニトリル及び10gジエチレングリコールモノエチルエーテルアセテートからなる混合物を、1時間かけて滴下した。滴下終了後、さらに6時間重合反応を行った。その後、1gのハイドロキノンモノメチルエーテルを添加して、重合反応を停止した。引き続き、5gのグリシジルメタクリレート、1gのトリエチルベンジルアンモニウムクロライド及び10gのジエチレングリコールモノエチルエーテルアセテートからなる混合物を、0.5時間かけて滴下した。滴下終了後、さらに2時間付加反応を行った。得られた反応溶液をメタノールで精製することで未反応不純物を除去し、さらに24時間真空乾燥することで感光性有機化合物B-2を得た。
“IRGACURE”(登録商標) 369(チバジャパン株式会社製)
(溶剤)
ジエチレングリコールモノブチルエーテル(東京化成工業株式会社製)
(導電性粒子A)
湿式還元法により製造されたAg粒子(体積平均粒子径:1.19μm、比表面積:1.12m2/g、タップ密度:4.8g/cm3)
(イオン吸着剤D)
・D-1 : ハイドロタルサイト DHT-4A(Mg4.5Al2(OH)13CO3・3.5H2O 協和化学工業社製)
・D-2 : 酸化マグネシウム-酸化アルミニウム複合酸化物“キョーワード”(登録商標)2000(Mg0.7Al0.3O1.15 協和化学工業社製)
・D-3 : 酸化マグネシウム(協和化学工業社製)
・D-4 : 活性炭粉末(Cas番号.7440-44-0 東京化成工業製)
・D-5 : リン酸ジルコニウム(共立マテリアル社製)
(エポキシ樹脂C-1)
・エポキシエステル80MFA(共栄社化学株式会社製、全塩素含有量300ppm以上)
(実施例1)
100mLボトルに、20gの感光性有機化合物B-1、4gのエポキシエステル80MFA、12gのN-n-ブトキシメチルアクリルアミド、4gの“IRGACURE”(登録商標) 369及び10gのジエチレングリコールモノブチルエーテルを入れ、自転公転ミキサー(ハイブリッドミキサー)“あわとり練太郎”(登録商標)(ARE-310;株式会社シンキー社製)で混合し、感光性樹脂溶液とした。得られた感光性樹脂溶液に、Ag粒子及びイオン吸着剤D-1を表1の重量%になるようにそれぞれ混ぜ合わせ、3本ローラー(EXAKT M-50;EXAKT社製)を用いて混練して、感光性導電ペーストを得た。得られた感光性導電ペーストについて、以下の評価をそれぞれ実施した。評価結果は、表1に示す。
膜厚50μmのPETフィルム上に感光性導電ペーストをスクリーン印刷法で塗布し、得られた塗布膜を100℃の乾燥オーブン内で10分間乾燥した。一定のラインアンドスペース(以下、L/S)で配列された直線群すなわち透光パターンを1つのユニットとし、L/Sの値が異なる9種類のユニットをそれぞれ有するフォトマスクを介して乾燥後の塗布膜を露光、現像して、L/Sの値が異なるパターンをそれぞれ得た。その後、得られた9つのパターンを140℃で30分間乾燥オーブン内でいずれもキュアして、L/Sの値が異なる導電パターンをそれぞれ得た。なお、フォトマスクが有する各ユニットのL/Sの値は、500/500、250/250、100/100、50/50、40/40、30/30、25/25、20/20、17/17、15/15、10/10とした(それぞれ、ライン幅(μm)/間隔(μm)を表す)。得られた導電パターンを光学顕微鏡で観察し、パターン間に残渣がなく、かつパターン剥がれのないL/Sの値が最小の導電パターンを確認し、そのL/Sの値を、現像可能なL/Sの値とした。このとき、現像可能なL/Sの値が30/30、25/25、20/20、17/17、15/15又は10/10の場合を◎、現像可能なL/Sの値が100/100、50/50又は40/40の場合を○、現像可能なL/Sの値が500/500又は250/250の場合を×、とそれぞれ判定した。なお、露光は露光装置(PEM-6M;ユニオン光学株式会社製)を用いて露光量200mJ/cm2(波長365nm換算)の全線露光を行い、現像は0.25重量%のNa2CO3水溶液に基板を30秒浸漬させた後、超純水によるリンス処理を施して行った。
ITO付きPETフィルム“ELECRYSTA”(登録商標)V270L-TFS(日東電工(株)製)上に感光性導電ペーストを乾燥後の塗布膜の膜厚が7μmになるようにスクリーン印刷法で塗布し、得られた塗布膜を90℃の乾燥オーブン内で10分間乾燥してからその全面を露光した。なお、露光の条件は、上記加工性評価と同様とした。その後、140℃で1時間乾燥オーブン内で加熱してから、1mm幅で10×10の碁盤目状にカッターで切れ目を入れた。このサンプルの碁盤目状の切れ目部位全体にセロハンテープ(ニチバン(株)製)を貼着して剥がし、残存マス数をカウントして初期評価をした。続いて、85℃、85%RHの恒温恒湿槽SH-661(エスペック(株)製)にサンプルを240時間投入し、取り出したサンプルの碁盤目状の切れ目部位全体にセロハンテープを貼着して剥がし、残存マス数をカウントして恒温恒湿槽投入後の評価をした。初期評価及び恒温恒湿槽投入後の評価ともに、残存マス数が95以上の場合を◎、残存マス数が70以上95未満の場合を○、残存マス数が70未満の場合を×、とそれぞれ判定した。
50gの感光性導電ペーストをテーブルトップ遠心機(2420;久保田商事株式会社製)に入れ、3000rpmで30分間遠心分離した。遠心分離後の上澄み溶液を150℃で10時間乾燥させてから、溶剤で100倍に希釈し、固層抽出用カートリッジ(GL-PaKPLS-3;GLサイエンス社製)でろ過したろ液について、塩素・硫黄分析装置(TOX-2100H;三菱アナリテック社製)を用いて全塩素含有量を測定した。
表1に示す組成の感光性導電ペーストを実施例1と同様の方法で製造し、評価結果を同じく表1に示した。
表1に示す組成の感光性導電ペーストを実施例1と同様の方法で製造し、評価結果を同じく表1に示した。
Claims (5)
- 導電性粒子Aと、
感光性有機化合物Bと、
エポキシ樹脂Cと、
ハイドロタルサイト、酸化マグネシウム、酸化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、炭酸マグネシウム、酸化ジルコニウム、ケイ酸マグネシウム、二酸化ケイ素、ゼオライト及び炭素系粉末からなる群から選ばれるイオン吸着剤Dと、を含む、感光性導電ペースト。 - 前記導電性粒子Aは、貴金属粒子である、請求項1記載の感光性導電ペースト。
- 請求項1又は2記載の感光性導電ペーストから形成された導電層を具備する、積層基板。
- 請求項1又は2記載の感光性導電ペーストを基板上に塗布して塗布膜を得る、塗布工程と、
前記塗布膜を乾燥する、乾燥工程と、
乾燥後の前記塗布膜を露光する、露光工程と、
露光後の前記塗布膜を現像して、パターンを得る、現像工程と、
前記パターンを加熱して、導電パターンを得る、加熱工程と、を備える、導電パターンの製造方法。 - 請求項1又は2記載の感光性導電ペーストから形成された導電パターンを周囲配線として備え、該周囲配線が、100μmピッチ以下である、静電容量型タッチパネル。
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JP2013550699A JP6225708B2 (ja) | 2012-11-13 | 2013-10-31 | 静電容量型タッチパネル |
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JP2018097249A (ja) * | 2016-12-15 | 2018-06-21 | Dic株式会社 | レジスト用感光性樹脂組成物の製造方法 |
WO2018155053A1 (ja) * | 2017-02-23 | 2018-08-30 | 京セラ株式会社 | 配線基板、電子装置用パッケージおよび電子装置 |
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JP2020111651A (ja) * | 2019-01-09 | 2020-07-27 | 凸版印刷株式会社 | 塗布剤、印刷物及び印刷物の製造方法 |
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US20150248053A1 (en) | 2015-09-03 |
KR101971899B1 (ko) | 2019-04-24 |
JPWO2014077136A1 (ja) | 2017-01-05 |
TW201419313A (zh) | 2014-05-16 |
JP6225708B2 (ja) | 2017-11-08 |
KR20150086268A (ko) | 2015-07-27 |
TWI592949B (zh) | 2017-07-21 |
US9846361B2 (en) | 2017-12-19 |
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