WO2015122345A1 - 導電ペースト、パターンの製造方法、導電パターンの製造方法及びセンサー - Google Patents
導電ペースト、パターンの製造方法、導電パターンの製造方法及びセンサー Download PDFInfo
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- WO2015122345A1 WO2015122345A1 PCT/JP2015/053229 JP2015053229W WO2015122345A1 WO 2015122345 A1 WO2015122345 A1 WO 2015122345A1 JP 2015053229 W JP2015053229 W JP 2015053229W WO 2015122345 A1 WO2015122345 A1 WO 2015122345A1
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- conductive
- pattern
- silver
- conductive paste
- conductive pattern
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
-
- 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
- G03F7/20—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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
- G03F7/2024—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure of the already developed image
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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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
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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
- 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
-
- 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
- H05K3/027—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 the conductive material being removed by irradiation, e.g. by photons, alpha or beta particles
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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
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0218—Composite particles, i.e. first metal coated with second metal
-
- 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
-
- 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
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0783—Using solvent, e.g. for cleaning; Regulating solvent content of pastes or coatings for adjusting the viscosity
Definitions
- the present invention relates to a conductive paste, a pattern manufacturing method, a conductive pattern manufacturing method, and a sensor.
- an organic-inorganic composite conductive pattern including a resin that is an organic component and a conductive filler that is an inorganic component, a large amount of silver flakes, copper powder, or carbon particles is mixed in a resin or an adhesive.
- a so-called polymer-type conductive paste has been put into practical use.
- conductive patterns can be obtained by heating and curing a pattern formed by a screen printing method (Patent Documents 1 and 2). However, it is difficult to accurately form a conductive pattern having a width of 100 ⁇ m or less.
- Patent Document 3 a conductive paste capable of acid etching (Patent Document 3) and a photosensitive curable conductive paste containing silver particles as conductive particles have been developed (see Patent Documents 4 and 5).
- the conductive paste capable of acid etching has a problem that the manufacturing process is complicated because it is necessary to form a resist layer when forming the conductive pattern.
- a conventional photosensitive curable conductive paste can form a high-definition conductive pattern having a width of 100 ⁇ m or less.
- the silver particles used are expensive and the short circuit of the conductive pattern due to the ion migration phenomenon has been regarded as a problem.
- an object of the present invention is to provide a conductive paste that can form a conductive pattern in which the occurrence of the ion migration phenomenon is remarkably suppressed and is low in cost.
- the present invention provides a conductive paste, a pattern manufacturing method, a conductive pattern manufacturing method, and a sensor described in the following (1) to (7).
- a conductive paste comprising silver-coated particles in which conductive nuclei are coated with silver and a photosensitive organic compound, wherein the proportion of silver in the silver-coated particles is 10 to 45% by mass.
- the conductive paste according to (1) or (2), wherein the ratio of the silver-coated particles in the total solid content is 40 to 80% by mass.
- a pattern manufacturing method in which the conductive paste according to any one of (1) to (3) above is applied onto a substrate, exposed and developed to obtain a pattern with a line width of 2 to 50 ⁇ m.
- the conductive paste according to any one of (1) to (3) above is applied onto a substrate, exposed and developed to obtain a pattern with a line width of 2 to 50 ⁇ m, and the pattern is formed at 100 to 300 ° C.
- the conductive paste according to any one of (1) to (3) above is applied on a substrate, exposed and developed to obtain a pattern with a line width of 2 to 50 ⁇ m, and the obtained pattern is further converted into xenon.
- the conductive paste of the present invention it is possible to form a high-definition conductive pattern that is low in cost and has an ion migration phenomenon remarkably suppressed.
- the conductive paste of the present invention contains silver-coated particles in which conductive nuclei are coated with silver and a photosensitive organic compound, and the proportion of silver in the silver-coated particles is 10 to 45% by mass. It is characterized by.
- the conductive pattern formed by the method for producing a conductive pattern of the present invention is a composite of an organic component and an inorganic component, and when heated at 100 to 300 ° C. or when exposed to light from a xenon flash lamp.
- the silver-coated particles, which are inorganic components come into contact with each other due to curing shrinkage of the photosensitive organic compound, which is an organic component, so that conductivity is exhibited.
- the conductive paste of the present invention contains silver-coated particles in which conductive nuclei are coated with silver.
- the ion migration phenomenon refers to a phenomenon in which a metal component affected by an electric field moves on the surface or inside of a non-metallic substance at a low temperature of less than 100 ° C.
- silver is known to be most susceptible to ion migration.
- the conductive core is a particle of a substance that conducts electricity.
- a metal nucleus having good electrical conductivity is preferable.
- the metal constituting the conductive core include particles of copper, lead, tin, nickel, zinc, aluminum, tungsten, molybdenum, ruthenium oxide, chromium, titanium, indium, alloys of these metals, or composites of these metals. Is mentioned. From the viewpoint of conductivity and cost, copper, zinc, nickel, aluminum, or an alloy thereof is preferable, and copper, zinc, nickel, or an alloy thereof is more preferable. Among these, it is preferable to contain copper. In an alloy of copper and zinc, or an alloy of copper and nickel, the proportion of zinc or nickel in the conductive core is preferably 1 to 50% by mass in order to prevent the acid value of the copper component.
- the volume average particle diameter of the silver-coated particles is preferably 0.1 to 10 ⁇ m, and more preferably 0.5 to 6 ⁇ m.
- the volume average particle size is 0.1 ⁇ m or more, the contact probability between silver-coated particles when exposed at 100 to 300 ° C. or exposed to light from a xenon flash lamp is improved, and the specific resistance of the formed conductive pattern and The disconnection probability is low. Furthermore, in the exposure of the coating film of the conductive paste applied on the substrate, the exposure light can smoothly pass through the coating film, and fine patterning is facilitated.
- the volume average particle diameter is 10 ⁇ m or less, the surface smoothness, pattern accuracy and dimensional accuracy of the formed conductive pattern are improved.
- the volume average particle diameter can be measured by a Coulter counter method.
- the proportion of silver in the silver-coated particles needs to be 10 to 45% by mass.
- the proportion of silver in the silver-coated particles is 10% by mass or more, a conductive pattern having low specific resistance and high stability can be formed. Furthermore, when the content is 20% by mass or more, a pattern having a lower specific resistance can be formed.
- the proportion of silver in the silver-coated particles exceeds 45% by mass, the cost of the silver-coated particles increases and the effect of suppressing the ion migration phenomenon decreases. Further, when the proportion of silver in the silver-coated particles is 10 to 45% by mass, the viscosity of the conductive paste can be suitably adjusted.
- the proportion of silver in the silver-coated particles and the composition of the conductive core were determined by applying a load to the silver-coated particles and molding them into pellets, using a fluorescent X-ray device (manufactured by Rigaku Corporation) in a vacuum atmosphere. It can be calculated by measuring with ZSX (Priumus).
- the surface of the conductive core is completely covered in order to suppress a chemical reaction between the conductive core and the photosensitive organic compound contained in the conductive paste.
- a part of the surface of the conductive core may be coated, or a hole may be formed in the silver coating film.
- the conductive paste contains a photosensitive organic compound having a carboxyl group
- the conductive nucleus contains a metal that is easily cationized, such as copper, zinc or nickel, the conductive nucleus and the carboxyl group are formed.
- the viscosity of the conductive paste may increase significantly or the conductive paste may gel. For this reason, the aspect in which the surface of the conductive core is sufficiently covered with chemically stable silver is preferable.
- a chemical reduction method using a substitution reaction between the conductive core and silver or as another chemical reduction method, using a reducing agent together with silver or silver on the surface of the conductive core.
- a method of depositing a silver precursor and a physical method of electrically adsorbing silver particles to a conductive core and fixing them with pressure are preferable because silver is uniformly coated around the conductive core, and even a small particle diameter is easy to coat.
- a substitution reaction between the metal that is easily ionized and silver is more likely to occur, and the coating efficiency is further improved. For example, if the conductive core copper contains zinc or nickel which is more easily ionized, it is easy to uniformly coat silver. For this reason, it is good to use the silver covering particle produced by the chemical reduction method using a substitution reaction.
- Examples of the silver compound used for coating the conductive core include silver salts such as silver nitrate, silver acetate or silver chloride. These silver salts are preferably used after being dissolved in water or an organic solvent. Moreover, you may add a reducing agent, a chelating agent, or a pH adjuster as an additive.
- the ratio of silver-coated particles in the total solid content of the conductive paste of the present invention is preferably 40 to 80% by mass.
- the proportion of the total solid content is 40% by mass or more, the contact probability between silver coated particles is improved when heated at 100 to 300 ° C. or exposed to light from a xenon flash lamp, and the ratio of the formed conductive pattern Resistance and disconnection probability are reduced.
- the ratio of the total solid content is 80% by mass or less, in the exposure of the coating film of the conductive paste, the exposure light can smoothly pass through the coating film, and fine patterning becomes easy.
- the total solid content means all components of the conductive paste excluding the solvent.
- the photosensitive organic compound (hereinafter referred to as “compound (A)”) contained in the conductive paste of the present invention refers to a monomer, oligomer or polymer having one or more unsaturated double bonds.
- Examples of the compound (A) include an acrylic copolymer.
- the acrylic copolymer refers to a copolymer containing an acrylic monomer having a carbon-carbon double bond as a copolymer component.
- acrylic monomers having a carbon-carbon double bond examples include methyl acrylate, acrylic acid, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl acrylate, iso-butyl acrylate, iso-propane acrylate, glycidyl acrylate, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, Isobonyl acrylate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropen
- Styrenes ⁇ -methacryloxypropyltrimethoxy Silane, 1-vinyl-2-pyrrolidone, allylated cyclohexyl diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene Glycol diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, glycerol diacrylate, methoxylated cyclohexyl diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate, polypropylene glycol diacrylate, Triglycerol diacrylate, trimethyl Propane triacrylate, acrylic acid adduct of ethylene glycol diglycidyl ether having a hydroxyl
- a skeleton selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, and a hydrogenated bisphenol A skeleton.
- An alkali-soluble acrylic copolymer that dissolves in an alkali developer or the like can be obtained by using an unsaturated acid such as an unsaturated carboxylic acid as a monomer.
- unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetate, and acid anhydrides thereof.
- the acid value of the obtained acrylic copolymer can be adjusted by the amount of the unsaturated acid used.
- the acid value of the compound is preferably 40 to 250 mg KOH / g in order to optimize the alkali solubility of the compound.
- the acid value of the compound can be measured according to JIS K 0070 (1992).
- the conductive paste of the present invention preferably contains a nitrogen-containing compound.
- the nitrogen-containing compound hereinafter, “compound (B)” refers to a compound selected from the group consisting of imidazole, triazole, ethyleneimine, and oxime compounds.
- compound (B) refers to a compound selected from the group consisting of imidazole, triazole, ethyleneimine, and oxime compounds.
- the above-described effect may be more remarkably obtained when it coexists with the compound (B) than when it does not contain.
- changes over time such as increase in viscosity and gelation of the conductive paste can be suppressed. This is also effective when the coating is insufficient due to a hole in the silver coating film on the surface of the conductive core.
- Examples of the compound (B) include 2-hydroxy-4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 Benzotriazole compounds such as '-hydroxy-3', 5'-di-t-butylphenyl) -5-chlorobenzotriazole or 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, N- (2-aminoethyl) piperazine, 1- (2-aminoethyl) -4-methylpiperazine hydrochloride, 6-amino -1-methyluracil, polyethyleneimine, octadecyl isocyanate-modified poly
- the amount of compound (B) added to 100 parts by mass of compound (A) is preferably 0.01 to 20 parts by mass.
- the added amount with respect to 100 parts by mass of the compound (A) is 0.01 parts by mass or more, the conductivity of the pattern can be expressed by heating at a lower temperature, and the increase in viscosity with time and gelation of the conductive paste. Such a change with time can be suppressed.
- the addition amount is 20 parts by mass or less, fine patterning becomes easy.
- the conductive paste of the present invention preferably contains a thermosetting compound (hereinafter, “compound (C)”).
- the compound (C) include an epoxy resin, a novolac resin, a phenol resin, a polyimide precursor, or a closed ring polyimide.
- An epoxy resin is preferable for improving adhesion with the substrate and forming a highly stable conductive pattern. Note that the rigidity, toughness and flexibility of the pattern can be controlled by appropriately selecting the skeleton of the epoxy resin.
- the epoxy resin include ethylene glycol-modified epoxy resin, bisphenol A type epoxy resin, brominated epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, and novolac type epoxy resin. , Alicyclic epoxy resin, glycidylamine type epoxy resin, glycidyl ether type epoxy resin or heterocyclic epoxy resin.
- the amount of compound (C) added to 100 parts by weight of compound (A) is preferably 1 to 100 parts by weight, more preferably 10 to 80 parts by weight, and 30 to 80 parts by weight. Is more preferable. Adhesiveness with a board
- substrate improves that the addition amount with respect to 100 mass parts compound (A) is 1 mass part or more. On the other hand, when the addition amount is 100 parts by mass or less, a highly stable conductive pattern can be formed.
- the conductive paste of the present invention preferably contains a photopolymerization initiator.
- the photopolymerization initiator refers to a compound that decomposes by absorbing light having a short wavelength such as ultraviolet rays or generates a radical by causing a hydrogen abstraction reaction.
- 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) -phenylphosphine 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′-methyl Diphenyl ketone, dibenzyl ketone, fluorenone, 2,2'-diethoxyacetophenone 2,2-dimethoxy
- the addition amount of the photopolymerization initiator with respect to 100 parts by mass of the compound (A) is preferably 0.05 to 30 parts by mass, and more preferably 5 to 20 parts by mass.
- the addition amount with respect to 100 parts by mass of the compound (A) is 0.05 parts by mass or more, the cured density of the exposed part of the coating film of the conductive paste increases, and the residual film rate after development increases.
- the addition amount is 30 parts by mass or less, excessive light absorption at the upper part of the coating film of the conductive paste is suppressed. As a result, a decrease in adhesion to the substrate due to the formed conductive pattern having an inversely tapered shape is suppressed.
- the 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 with respect to 100 parts by mass of the compound (A) is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 10 parts by mass. Photosensitivity improves enough that the addition amount with respect to 100 mass parts compound (A) is 0.05 mass part. On the other hand, when the addition amount is 10 parts by mass or less, excessive light absorption at the upper part of the coating film of the conductive paste is suppressed. As a result, a decrease in adhesion to the substrate due to the formed conductive pattern having an inversely tapered shape is suppressed.
- the conductive paste of the present invention may contain a solvent.
- the viscosity of the conductive paste can be appropriately adjusted by mixing the solvent.
- the solvent may be added last in the process of preparing the paste. By increasing the amount of solvent, the film thickness of the conductive film after drying can be reduced.
- the solvent examples include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate (hereinafter, “ DMEA "), diethylene glycol monomethyl ether acetate, ⁇ -butyrolactone, ethyl lactate, ethylene glycol mono-n-propyl ether or propylene glycol monomethyl ether acetate.
- DMEA diethylene glycol monomethyl ether acetate
- ⁇ -butyrolactone diethylene glycol monomethyl ether acetate
- ⁇ -butyrolactone ethyl lactate
- ethylene glycol mono-n-propyl ether or propylene glycol monomethyl ether acetate In order to increase the stability of the conductive paste, an organic solvent having a hydroxyl group is preferred.
- organic solvent having a hydroxyl group examples include terpineol, dihydroterpineol, hexylene glycol, 3-methoxy-3-methyl-1-butanol (hereinafter “Solfit”), 2,2,4-trimethyl-1, 3-pentanediol monoisobutyrate, triethylene glycol monobutyl ether, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monobutyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol butyl ether, diethylene glycol ethyl ether, tripropylene glycol methyl ether, Tripropylene glycol n-butyl ether, propylene glycol phenyl ether, propylene glycol methyl ether, Pyrene glycol ethyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropy
- the viscosity of the conductive paste may be within a range that can be applied, and the viscosity of the conductive paste when applied by screen printing is 4,000 to 150,000 mPa ⁇ s as a value measured at 3 rpm using a Brookfield viscometer. s is preferable, and 4,000 to 50,000 mPa ⁇ s is more preferable. If the viscosity is less than 4,000 mPa ⁇ s, a coating film may not be formed on the substrate. In this case, it is preferable to use a method such as spin coating using a spinner, spray coating, roll coating, offset printing, gravure printing, or die coater. On the other hand, when the viscosity exceeds 150,000 mPa ⁇ s, unevenness is generated on the surface of the coating film, and uneven exposure is likely to occur.
- the conductive paste of the present invention may contain an additive such as a plasticizer, a leveling agent, a surfactant, a silane coupling agent, an antifoaming agent, or a pigment as long as the desired properties are not impaired. .
- 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 conductive paste of the present invention is manufactured using a dispersing machine or a kneader such as a three-roller, ball mill or planetary ball mill.
- the conductive paste of the present invention is applied on a substrate, exposed and developed to obtain a pattern having a line width of 2 to 50 ⁇ m.
- the conductive paste of the present invention is applied on a substrate, exposed and developed to obtain a pattern with a line width of 2 to 50 ⁇ m.
- a conductive pattern is obtained by heating at 300 ° C. Further, instead of heating at 100 to 300 ° C., a conductive pattern can also be obtained by exposing with light from a xenon flash lamp.
- the substrate examples include a polyethylene terephthalate film (hereinafter referred to as “PET film”), a polyimide film, a polyester film, an aramid film, an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone resin substrate, and a glass substrate.
- PET film polyethylene terephthalate film
- a silicon wafer an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, a decorative layer forming substrate, or an insulating layer forming substrate.
- Examples of the method for applying the conductive paste of the present invention to a 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. What is necessary is just to determine the film thickness of the coating film obtained suitably according to the coating method or the total solid content concentration or viscosity of the conductive paste.
- the film thickness after drying is preferably 0.1 to 50 ⁇ m.
- the conductive paste of the present invention is preferably applied by screen printing.
- the film thickness can be measured by using a stylus step meter 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.
- a stylus step meter 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.
- the conductive paste of the present invention contains a solvent
- 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 or infrared rays.
- the heating temperature is preferably 50 to 180 ° C., and the heating time is preferably 1 minute to several hours.
- the obtained coating film is exposed by a photolithography method through a pattern forming mask.
- 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 coating film having a line width of 2 to 50 ⁇ m can be formed on the substrate by developing the exposed coating film using a developer and dissolving and removing the unexposed portion.
- Examples of the development method include alkali development and organic development.
- Examples of 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.
- aqueous solution of aminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine may be mentioned.
- polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or ⁇ -butyrolactone
- alcohols such as methanol, ethanol or isopropanol
- ethyl lactate Alternatively, esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone, or a surfactant may be added.
- Examples of the developer for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoryl
- Examples thereof include polar solvents such as amides or mixed solutions of these polar solvents and 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 curing heating temperature is preferably 100 to 180 ° C.
- the heating temperature is less than 100 ° C., the curing shrinkage of a photosensitive organic compound or the like that is an organic component becomes insufficient, and the specific resistance cannot be lowered.
- the heating temperature exceeds 300 ° C., a substrate having low heat resistance cannot be used.
- the heating temperature is preferably 180 ° C. or lower.
- the heating time is preferably 1 minute to several hours. Examples of the method for heating the obtained pattern include heat drying or vacuum drying using an oven, an inert oven, a hot plate, infrared rays, or the like.
- the light irradiation of the xenon flash lamp is preferably pulse irradiation, and the irradiation energy per pulse is more preferably 2.0 J / cm 2 or less.
- heating at 100 to 300 ° C. and exposure with light from a xenon flash lamp may be performed in combination.
- the conductive pattern manufactured using the conductive paste of the present invention and the conductive pattern manufactured by the method of manufacturing the conductive pattern of the present invention are preferably used as a sensor, particularly a detection sensor for a peripheral wiring for a touch panel or a touch panel display unit.
- Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. Since the capacitance type touch panel particularly requires fine wiring, the conductive paste of the present invention capable of fine processing of 50 ⁇ m or less is more preferably used.
- the frame width can be narrowed and the display portion can be widened.
- the display part of the touch panel provided with the conductive pattern of the present invention as a detection sensor having a width of 10 ⁇ m or less it is possible to achieve suitable visibility even at a low cost.
- ⁇ Patternability evaluation method> The conductive paste was applied onto the substrate so that the thickness of the dry film was 5 ⁇ m, and the obtained conductive paste coating film was dried in a drying oven at 100 ° C. for 5 minutes.
- a linear light-transmitting pattern arranged in a certain line and space (hereinafter referred to as “L / S”) is defined as one unit, and dried through a photomask having nine types of units each having a different L / S value.
- the subsequent coating film was exposed and developed to obtain nine types of 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, 15 / 15, 10/10, 8/8, and 5/5 (representing line width ( ⁇ m) / interval ( ⁇ m), respectively).
- the obtained pattern was observed with an optical microscope, a pattern having no residue between the patterns and no pattern peeling was confirmed, and the L / S value was determined as the developable L / S.
- the value of The exposure was performed using an exposure apparatus (PEM-6M; manufactured by Union Optical Co., Ltd.) with an exposure amount of 150 mJ / cm 2 (wavelength 365 nm conversion), and the development was performed with a 0.2 mass% Na 2 CO 3 solution.
- the substrate was immersed for 30 seconds, and then rinsed with ultrapure water.
- the conductive paste was applied onto the substrate so that the thickness of the dry film was 5 ⁇ m, and the obtained conductive paste coating film was dried in a drying oven at 100 ° C. for 5 minutes. The coating film after drying was exposed and developed through a photomask to obtain a pattern. The obtained pattern was heated at 140 ° C. for 30 minutes (however, when a PET substrate was used, a 0.3 msec xenon flash lamp was irradiated with an irradiation energy of 1.0 J / cm 2 ). A conductive pattern for specific resistance measurement was obtained. The obtained conductive pattern had a line width of 0.400 mm and a line length of 80 mm.
- the exposure and development conditions were the same as in the patterning evaluation method.
- a resistance value was measured by connecting each end of the obtained conductive pattern for measuring specific resistance with a resistance meter, and the specific resistance was calculated based on the following formula (1).
- Specific resistance resistance value ⁇ film thickness ⁇ line width / line length (1)
- the line width is an average value obtained by observing the line widths at three random positions with an optical microscope and analyzing the image data.
- ⁇ Migration resistance evaluation method> The conductive paste was applied onto the substrate so that the thickness of the dry film was 5 ⁇ m, and the obtained conductive paste coating film was dried in a drying oven at 100 ° C. for 5 minutes. The coating film after drying was exposed and developed through a photomask having a comb pattern to obtain a comb pattern. The obtained comb pattern is heated at 140 ° C. for 30 minutes (however, when a PET substrate is used, it is irradiated with light of a 0.3 msec xenon flash lamp with an irradiation energy of 1.0 J / cm 2 ). To obtain a conductive pattern for evaluating migration resistance. The line width of the obtained conductive pattern was 50 ⁇ m, the space width between the lines was 50 ⁇ m, and the line length was 40 mm.
- the exposure and development conditions were the same as in the patterning evaluation method.
- a current was applied at an applied voltage of DC 20 V, and a constant temperature and humidity of 85 ° C. and 85 RH%.
- the change in the conductive pattern after exposure for 60 minutes was observed, and the case where dendrid or a short circuit occurred was determined as B, and the case where there was no change was determined as A.
- the obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum-dried for 24 hours to obtain a compound (A-1) having a carboxyl group and an unsaturated double bond.
- the acid value of the obtained compound (A-1) was 103 mgKOH / g.
- the obtained reaction solution was purified with methanol to remove unreacted impurities, and further vacuum-dried for 24 hours to obtain a compound (A-4) having a carboxyl group and an unsaturated double bond.
- the acid value of the obtained compound (A-4) was 101 mgKOH / g.
- Silver-coated particles shown in Table 1 [Photopolymerization initiator] IRGACURE (registered trademark) 369 (hereinafter referred to as “IC369”) (manufactured by BASF Japan Ltd.) N-1919 (manufactured by ADEKA Corporation) [monomer] Light acrylate BP-4EA (manufactured by Kyoeisha Chemical Co., Ltd.) [solvent] DMEA (manufactured by Tokyo Chemical Industry Co., Ltd.) Solfit (manufactured by Kuraray Co., Ltd.) Example 1 Put 100 g of Compound (A-1), 0.50 g of IC369 and 23.5 g of DMEA into a 100 mL clean bottle, and use “Awatori Rentaro” (registered trademark) (ARE-310; manufactured by Shinky Corporation) ) To obtain 34 g of a resin solution (solid content: 50% by mass). The composition is shown in Table 1.
- the developable L / S value which is an evaluation index of patterning property, was 15/15 ⁇ m, and it was confirmed that favorable pattern processing was performed.
- the specific resistance of the conductive pattern was 7.2 ⁇ 10 ⁇ 5 ⁇ cm. Table 3 shows the results of the evaluation.
- Examples 2 to 9, 12 to 15 A conductive paste having the composition shown in Table 1 was produced by the same method as in Example 1, and the results of the same evaluation as in Example 1 are shown in Table 3.
- Example 3 shows the results of the same evaluation as in Example 1 except that a conductive paste having the composition shown in Table 1 was manufactured in the same manner as in Example 1, and the xenon flash lamp was irradiated instead of heating. Show.
- the electrically conductive paste of this invention can be utilized suitably for manufacture of electrically conductive patterns, such as a detection sensor of the display part for touchscreens, or surrounding wiring for touchscreens.
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Abstract
Description
(1) 導電性の核を銀で被覆した銀被覆粒子、及び、感光性有機化合物、を含有し、上記銀被覆粒子に占める銀の割合が、10~45質量%である、導電ペースト。
(2) 上記導電性の核が、銅を含有する、上記(1)に記載の導電ペースト。
(3) 全固形分に占める上記銀被覆粒子の割合が、40~80質量%である、上記(1)又は(2)に記載の導電ペースト。
(4) 上記(1)~(3)のいずれかに記載の導電ペーストを基板上に塗布し、露光及び現像し、線幅が2~50μmのパターンを得る、パターンの製造方法。
(5) 上記(1)~(3)のいずれかに記載の導電ペーストを基板上に塗布し、露光及び現像し、線幅が2~50μmのパターンを得て、パターンを100~300℃で加熱して、導電パターンを得る、導電パターンの製造方法。
(6) 上記(1)~(3)のいずれかに記載の導電ペーストを基板上に塗布し、露光及び現像し、線幅が2~50μmのパターンを得て、さらに得られたパターンをキセノンフラッシュランプの光で露光して、導電パターンを得る、導電パターンの製造方法。
(7) 上記(1)~(3)のいずれかに記載の導電ペーストを用いて製造された導電パターンを具備する、センサー。
(8) 上記(5)又は(6)記載の導電パターンの製造方法で製造された導電パターンを具備する、センサー。
基板上に導電ペーストを乾燥膜の膜厚が5μmになるように塗布し、得られた導電ペーストの塗布膜を100℃の乾燥オーブン内で5分間乾燥した。一定のラインアンドスペース(以下、「L/S」)で配列された直線状の透光パターンを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及び現像して、L/Sの値が異なる9種類の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、15/15、10/10、8/8、5/5とした(それぞれ線幅(μm)/間隔(μm)を表す)。得られた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。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150mJ/cm2(波長365nm換算)で全線露光を行い、現像は0.2質量%のNa2CO3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。
基板上に導電ペーストを乾燥膜の膜厚が5μmになるように塗布し、得られた導電ペーストの塗布膜を100℃の乾燥オーブン内で5分間乾燥した。フォトマスクを介して乾燥後の塗布膜を露光及び現像して、パターンを得た。得られたパターンを140℃で30分間加熱して(ただしPET基板を用いた場合には、1.0J/cm2の照射エネルギーで0.3msecキセノンフラッシュランプの光を照射して)導電性を発現させ、比抵抗測定用の導電パターンを得た。得られた導電性パターンの線幅は0.400mmであり、ライン長さは80mmであった。
比抵抗 = 抵抗値×膜厚×線幅/ライン長 ・・・ (1)
なお、線幅は、ランダムな3つの位置の線幅を光学顕微鏡で観察し、画像データを解析して得られた平均値である。
基板上に導電ペーストを乾燥膜の膜厚が5μmになるように塗布し、得られた導電ペーストの塗布膜を100℃の乾燥オーブン内で5分間乾燥した。櫛形パターンを有するフォトマスクを介して乾燥後の塗布膜を露光及び現像して、櫛形パターンを得た。得られた櫛形パターンを140℃で30分間加熱して(ただしPET基板を用いた場合には、1.0J/cm2の照射エネルギーで0.3msecキセノンフラッシュランプの光を照射して)導電性を発現させ、マイグレーション耐性評価用の導電パターンを得た。得られた導電性パターンの線幅は50μmであり、ライン間のスペース幅は50μmであり、ライン長さは40mmであった。
<導電ペーストの経時状態変化の評価方法>
混練後と2週間保管後の導電ペーストの状態がほとんど変化なく、粘性を帯び、塗布が可能なものをS、導電ペースト保管容器の底に塊を生じるなど、やや固形分の分離を生じているが、混ぜることで塗布が可能なものをA、導電ペースト全体が著しく固く、混ぜるのが困難か、ゲル化することによって、塗布ができないものをBとした。また、混練後1時間以内に固化を始め、塗布ができない程度に変化したものもBとした。
(合成例1)
共重合比率(質量基準):エチルアクリレート(以下、「EA」)/メタクリル酸2-エチルヘキシル(以下、「2-EHMA」)/スチレン(以下、「St」)/グリシジルメタクリレート(以下、「GMA」)/アクリル酸(以下、「AA」)=20/40/20/5/15
窒素雰囲気の反応容器中に、150gのDMEA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EA、40gの2-EHMA、20gのSt、15gのAA、0.8gの2,2’-アゾビスイソブチロニトリル及び10gのDMEA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GMA、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DMEA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、カルボキシル基及び不飽和二重結合を有する化合物(A-1)を得た。得られた化合物(A-1)の酸価は103mgKOH/gであった。
共重合比率(質量基準)トリシクロデカンジメタノールジアクリレート(IRR214-K;ダイセル・サイテック(株)製)/変性ビスフェノールAジアクリレート(EBECRYL150;ダイセル・サイテック(株)製)/St/AA)=25/40/20/15
窒素雰囲気の反応容器中に、150gのDMEAを仕込み、オイルバスを用いて80℃まで昇温した。これに、25gのIRR214-K、40gのEBECRYL150、20gのSt、15gのAA、0.8gの2,2’-アゾビスイソブチロニトリル及び10gのDMEA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。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、カルボキシル基及び不飽和二重結合を有する化合物(A-2)を得た。得られた化合物(A-2)の酸価は89mgKOH/gであった。
共重合比率(質量基準):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)製)/EA/GMA/AA=50/10/5/15
窒素雰囲気の反応容器中に、150gのDMEA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、20gのEA、15gのAA、0.8gの2,2’-アゾビスイソブチロニトリル及び10gのDMEA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GMA、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DMEA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、カルボキシル基及び不飽和二重結合を有する化合物(A-3)を得た。得られた化合物(A-3)の酸価は96mgKOH/gであった。
共重合比率(質量基準)2官能エポキシアクリレートモノマー(エポキシエステル3002A;共栄社化学(株)製)/2官能エポキシアクリレートモノマー(エポキシエステル70PA;共栄社化学(株)製)/GMA/St/AA=20/40/5/20/15
窒素雰囲気の反応容器中に、150gのDMEAを仕込み、オイルバスを用いて80℃まで昇温した。これに、20gのエポキシエステル3002A、40gのエポキシエステル70PA、20gのSt、15gのAA、0.8gの2,2’-アゾビスイソブチロニトリル及び10gのDMEA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GMA、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DMEA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、カルボキシル基及び不飽和二重結合を有する化合物(A-4)を得た。得られた化合物(A-4)の酸価は101mgKOH/gであった。
(B-1)1-(2-アミノエチル)ピペラジン
(B-2)6-アミノ-1-メチルウラシル
(B-3)エポミン(登録商標)SP-200((株)日本触媒社製)
(B-4)ベンゾトリアゾール。
(C-1)エポキシ樹脂(JER828(エポキシ当量188);三菱化学(株)製)
(C-2)エポキシ樹脂(アデカレジンEPR-21(エポキシ当量210);(株):ADEKA製)。
表1に示す銀被覆粒子
[光重合開始剤]
IRGACURE(登録商標)369(以下、「IC369」)(BASFジャパン(株)製)
N-1919((株)ADEKA製)
[モノマー]
ライトアクリレートBP-4EA(共栄社化学(株)製)
[溶剤]
DMEA(東京化成工業(株)製)
ソルフィット((株)クラレ製)
(実施例1)
100mLクリーンボトルに、10.0gの化合物(A-1)、0.50gのIC369及び23.5gのDMEAを入れ、“あわとり錬太郎”(登録商標)(ARE-310;(株)シンキー製)で混合して、34gの樹脂溶液(固形分50質量%)を得た。組成を表1に示す。
表1に示す組成の導電ペーストを実施例1と同様の方法で製造し、実施例1と同様の評価を行った結果を表3に示す。
表1に示す組成の導電ペーストを実施例1と同様の方法で製造し、加熱に代えてキセノンフラッシュランプの光を照射した以外は、実施例1と同様の評価を行った結果を表3に示す。
表2に示す組成の導電ペーストを実施例1と同様の方法で製造し、実施例1と同様の評価を行った結果を表3に示す。
Claims (8)
- 導電性の核を銀で被覆した銀被覆粒子、及び、
感光性有機化合物、を含有し、
前記銀被覆粒子に占める銀の割合が、10~45質量%である、導電ペースト。 - 前記導電性の核が、銅を含有する、請求項1記載の導電ペースト。
- 全固形分に占める前記銀被覆粒子の割合が、40~80質量%である、請求項1又は2記載の導電ペースト。
- 請求項1~3のいずれか一項記載の導電ペーストを基板上に塗布し、露光及び現像し、線幅が2~50μmのパターンを得る、パターンの製造方法。
- 請求項1~3のいずれか一項記載の導電ペーストを基板上に塗布し、露光及び現像し、線幅が2~50μmのパターンを得て、さらに得られたパターンを100~300℃で加熱して、導電パターンを得る、導電パターンの製造方法。
- 請求項1~3のいずれか一項記載の導電ペーストを基板上に塗布し、露光及び現像し、線幅が2~50μmのパターンを得て、さらに得られたパターンをキセノンフラッシュランプの光で露光して、導電パターンを得る、導電パターンの製造方法。
- 請求項1~3のいずれか一項記載の導電ペーストを用いて製造された導電パターンを具備する、センサー。
- 請求項5又は6記載の導電パターンの製造方法で製造された導電パターンを具備する、センサー。
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CN201580007768.4A CN105960683A (zh) | 2014-02-12 | 2015-02-05 | 导电糊剂、图案的制造方法、导电图案的制造方法和传感器 |
KR1020167016538A KR20160122694A (ko) | 2014-02-12 | 2015-02-05 | 도전 페이스트, 패턴의 제조 방법, 도전 패턴의 제조 방법 및 센서 |
US15/117,744 US20160358688A1 (en) | 2014-02-12 | 2015-02-05 | Conductive paste, method of producing pattern, method of producing conductive paste, and sensor |
JP2015508906A JPWO2015122345A1 (ja) | 2014-02-12 | 2015-02-05 | 導電ペースト、パターンの製造方法、導電パターンの製造方法及びセンサー |
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JP (1) | JPWO2015122345A1 (ja) |
KR (1) | KR20160122694A (ja) |
CN (1) | CN105960683A (ja) |
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TWI746005B (zh) * | 2020-06-11 | 2021-11-11 | 瑋鋒科技股份有限公司 | 連續式異方性導電膠的製作方法 |
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- 2015-02-05 KR KR1020167016538A patent/KR20160122694A/ko not_active Application Discontinuation
- 2015-02-05 CN CN201580007768.4A patent/CN105960683A/zh active Pending
- 2015-02-05 JP JP2015508906A patent/JPWO2015122345A1/ja active Pending
- 2015-02-05 WO PCT/JP2015/053229 patent/WO2015122345A1/ja active Application Filing
- 2015-02-11 TW TW104104483A patent/TW201533534A/zh unknown
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TW201533534A (zh) | 2015-09-01 |
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JPWO2015122345A1 (ja) | 2017-03-30 |
US20160358688A1 (en) | 2016-12-08 |
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