WO2013146107A1 - 感光性導電ペーストおよび導電パターンの製造方法 - Google Patents
感光性導電ペーストおよび導電パターンの製造方法 Download PDFInfo
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- WO2013146107A1 WO2013146107A1 PCT/JP2013/055809 JP2013055809W WO2013146107A1 WO 2013146107 A1 WO2013146107 A1 WO 2013146107A1 JP 2013055809 W JP2013055809 W JP 2013055809W WO 2013146107 A1 WO2013146107 A1 WO 2013146107A1
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- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0277—Bendability or stretchability details
- H05K1/028—Bending or folding regions of flexible printed circuits
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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
- H05K1/0296—Conductive pattern lay-out details not covered by sub groups H05K1/02 - H05K1/0295
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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
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0145—Polyester, e.g. polyethylene terephthalate [PET], polyethylene naphthalate [PEN]
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
- H05K2201/10007—Types of components
- H05K2201/10151—Sensor
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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
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
- H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
- H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
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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
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/105—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
- H05K3/106—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam by photographic methods
Definitions
- the present invention relates to a photosensitive conductive paste and a method for producing a conductive pattern using the photosensitive conductive paste.
- the conductive pattern in the present invention refers to a conductive pattern containing both an organic component including a resin and an inorganic component including a conductive filler.
- Patent Documents 1 and 2 Most of the polymer-type conductive pastes in practical use form a pattern by a screen printing method and form a conductive pattern by heat curing.
- Patent Document 3 a conductive paste capable of acid etching (Patent Document 3) and a photosensitive curable conductive paste are disclosed (see Patent Documents 4 and 5).
- the conductive paste described in Patent Document 3 as a conventional technique has a problem that a resist layer needs to be formed on the coating film in order to perform patterning by a photolithography method, and the number of steps is increased.
- a fine pattern can be easily obtained by imparting photosensitivity, but in Patent Document 4, the conductivity is low, and in the method described in Patent Document 5, acrylic (methacrylic) is used for conductivity. It is necessary to reduce the equivalent, the conductive pattern obtained by this method is fragile, difficult to apply on a flexible substrate, and poor adhesion to an ITO (indium tin oxide) electrode on a glass or film substrate There was a problem.
- the object of the present invention is to solve the above-mentioned problems, have strong adhesion with ITO on the substrate, enable fine patterning, develop conductivity at a relatively low temperature, and in some cases have a flexible conductive pattern Is to obtain a photosensitive conductive paste and a method for producing a conductive pattern.
- the photosensitive conductive paste of the present invention has the following configuration. That is, a photosensitive conductive paste containing an epoxy acrylate (A) having a urethane bond, a photopolymerization initiator (B), and a conductive filler (C).
- A epoxy acrylate
- B photopolymerization initiator
- C conductive filler
- the manufacturing method of the conductive pattern of the present invention has the following configuration. That is, it is a method for producing a conductive pattern in which the photosensitive conductive paste is applied on a substrate, dried, exposed and developed, and then cured at a temperature of 100 ° C. or higher and 300 ° C. or lower.
- the epoxy acrylate (A) having a urethane bond preferably has a carboxyl group.
- the acid value of the epoxy acrylate (A) having a urethane bond is preferably in the range of 40 to 250 mgKOH / g.
- the epoxy acrylate (A) having the urethane bond preferably contains an unsaturated double bond.
- the epoxy acrylate (A) having a urethane bond preferably has a bisphenol A skeleton, a bisphenol F skeleton, a biphenyl skeleton, or a hydrogenated bisphenol A skeleton.
- the glass transition temperature of the epoxy acrylate (A) having a urethane bond is preferably in the range of ⁇ 10 to 60 ° C.
- the photosensitive conductive paste of the present invention preferably contains dicarboxylic acid or its acid anhydride (D).
- a conductive pattern having excellent adhesion with ITO, a low specific resistance even under low temperature curing conditions is obtained, and fine patterning is possible due to high photosensitive characteristics.
- a fine bump, wiring, etc. can be easily formed not only on a rigid board
- the photosensitive conductive paste of the present invention is obtained by dispersing a conductive filler (C) in a photosensitive resin composition comprising an epoxy acrylate having a urethane bond (A) and a photopolymerization initiator (B).
- the paste is applied onto the substrate, dried as necessary to remove the solvent, and then subjected to exposure, development, and a curing step at a temperature of 100 ° C. to 300 ° C. to obtain a desired conductive pattern on the substrate.
- It is a photosensitive conductive paste that can be used.
- the conductive pattern obtained by using the paste of the present invention is a composite of an organic component and an inorganic component, and conductivity is developed when the conductive fillers come into contact with each other by curing shrinkage during curing.
- the epoxy acrylate (A) having a urethane bond contained in the photosensitive conductive paste of the present invention refers to a compound having at least one hydroxyl group formed by ring-opening a urethane bond and an epoxy group in the molecule.
- the epoxy acrylate (A) having a urethane bond is an epoxy acrylate (a) obtained by reacting an epoxy compound with a monocarboxylic acid compound having an unsaturated double bond and a carboxyl group, a diisocyanate compound (b), and a diol compound (c). Is reacted to obtain an epoxy acrylate (A) having a urethane bond.
- the compound (A) which has a carboxyl group can be obtained by making the diol compound (c) into the diol compound which has a carboxyl group.
- the compound (A) which has an unsaturated double bond can be obtained by making the epoxy compound (d) which has an unsaturated double bond react with the epoxy acrylate (A) which has a urethane bond and a carboxyl group.
- epoxy acrylate (a) examples include epoxy ester 40EM (manufactured by Kyoeisha Chemical Co., Ltd.), epoxy ester 70PA (manufactured by Kyoeisha Chemical Co., Ltd.), epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.), epoxy ester 3002M ( Kyoeisha Chemical Co., Ltd.), CN104 (manufactured by Sartomer), CN121 (manufactured by Sartomer), EBECRYL3702 (manufactured by Daicel Cytec Co., Ltd.), EBECRYL3700 (manufactured by Daicel Cytec Co., Ltd.), EBECRYL600 (manufactured by Daicel Cytec (manufactured by Daicel Cytec)) Etc.).
- the diisocyanate compound (b) may be any compound having two isocyanate groups in the molecule. Specifically, toluene diisocyanate, diphenylmethane-4,4′-diisocyanate, hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene- Examples thereof include 1,5-diisocyanate, tridene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyanide diisocyanate, and norbornane diisocyanate.
- diol compound (c) examples include methanediol, 1,3-propanediol, 1,4-butanediol, benzenediol, 1,6-hexanediol, 1,2-cyclohexanediol, and 2-butene-1,4-diol.
- Butylethylpropanediol, 1,4-butynediol, and examples of the diol compound having a carboxyl group examples include dihydroxypropionic acid and 2,2-bis (hydroxymethyl) propionic acid.
- Examples of the epoxy compound (d) having an unsaturated double bond in the molecule include glycidyl acrylate and glycidyl methacrylate.
- the diol compound (c) having a carboxyl group is added to the epoxy acrylate (a), and the diisocyanate compound (b) is gradually added to carry out a urethanization reaction.
- a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by weight or less based on the reaction product.
- the reaction temperature at this time is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.
- a solvent or a thermal polymerization inhibitor may be used. While the reaction is appropriately sampled, the end point is the point at which absorption near 2250 cm ⁇ 1 in the infrared absorption spectrum of the sample ceases.
- an epoxy compound (d) having an unsaturated double bond in the molecule is added to the reaction solution obtained above, and an epoxy acrylate reaction with a diol compound (c) having a carboxyl group is performed.
- a basic catalyst can be used to promote the reaction, and the amount of the catalyst used is 10% by weight or less based on the reaction product.
- the reaction temperature at this time is 40 to 120 ° C., and the reaction time is preferably 5 to 60 hours.
- a solvent or a thermal polymerization inhibitor may be used.
- a catalyst to promote the reaction.
- the catalyst used include triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benztrimethylammonium iodide, triphenylphosphine. , Triphenylstibine, methyltriphenylstibine, chromium octoate, zirconium octoate and the like.
- the charge of each component is equivalent when the charge equivalent of the epoxy acrylate (a) is x equivalent, the charge equivalent of the diisocyanate compound (b) is y equivalent, and the charge equivalent of the diol compound (c) having a carboxyl group is z equivalent.
- the ratio is preferably in the range of 5 ⁇ (x + z) / y ⁇ 1.
- an isocyanate group remains at the terminal, which is not preferable because thermal stability is low and gelation may occur during storage.
- this value exceeds 5, the molecular weight is low, and there is a possibility that a problem of tackiness or a problem of low sensitivity may occur.
- the epoxy acrylate (A) having a urethane bond thus obtained can be developed with a solvent or an alkaline aqueous solution.
- the acid value of the compound (A) is preferably 40 to 250 mgKOH / g. If the acid value is less than 40 mgKOH / g, there is a problem that the solubility of the soluble part in the developer is lowered. On the other hand, if the acid value exceeds 250 mgKOH / g, the allowable development width cannot be increased.
- the acid value is determined according to JIS K 0070 (1992).
- the glass transition temperature of the epoxy acrylate (A) having a urethane bond contained in the photosensitive conductive paste of the present invention is preferably ⁇ 10 to 50 ° C., more preferably 10 to 40.
- Tg is ⁇ 10 ° C. or higher
- the tackiness of the dried film can be suppressed, and when it is 10 ° C. or higher, the shape stability particularly with respect to temperature change is increased.
- Tg is 50 ° C. or lower, flexibility is exhibited at room temperature, and when it is 50 ° C. or lower, internal stress at the time of bending can be relaxed, and generation of cracks can be particularly suppressed.
- the glass transition temperature of the epoxy acrylate (A) having a urethane bond contained in the photosensitive conductive paste of the present invention can be determined by differential scanning calorimetry (DSC) measurement of the photosensitive component, and this method is used in the present invention. It was.
- the photopolymerization initiator (B) contained in the photosensitive conductive paste of the present invention is a compound that absorbs light of a short wavelength such as ultraviolet rays and decomposes to generate a radical or a compound that generates a radical by causing a hydrogen abstraction reaction.
- 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, o-Benzoyl methyl benzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl ketone, di Benzyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2,2-dimethyl Xyl-2-pheny
- the addition amount of the photopolymerization initiator (B) is preferably 0.05 to 30 parts by weight, more preferably 5 to 20 parts per 100 parts by weight of the epoxy acrylate (A) having a urethane bond. Parts by weight.
- the addition amount of the photopolymerization initiator (B) is preferably 0.05 to 30 parts by weight, more preferably 5 to 20 parts per 100 parts by weight of the epoxy acrylate (A) having a urethane bond. Parts by weight.
- the amount of addition of the photopolymerization initiator (B) to 100 parts by weight of the compound (A) is 20 parts by weight or less, thereby suppressing excessive light absorption particularly at the upper part of the coating film by the photopolymerization initiator (B). And it can suppress that a conductive pattern becomes a reverse taper shape and adhesiveness with a base material falls.
- the photosensitive conductive paste of the present invention can be improved in sensitivity by adding a sensitizer together with the photopolymerization initiator (B), or can expand the wavelength range effective for the reaction.
- the 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) isonaphthothiazo
- the addition amount is usually preferably in the range of 0.05 to 10 parts by weight, more preferably 100 parts by weight of the compound (A). 0.1 to 10 parts by weight.
- the addition amount with respect to 100 parts by weight of the compound (A) 0.1 parts by weight or more, the effect of improving the photosensitivity is sufficiently exhibited, and the addition amount with respect to 100 parts by weight of the compound (A) is 10 parts by weight or less. By doing so, it is possible to suppress excessive light absorption particularly in the upper part of the coating film, the conductive pattern having a reverse taper shape, and a decrease in adhesion to the substrate.
- the conductive filler (C) contained in the photosensitive conductive paste of the present invention contains at least one of Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, ruthenium oxide, Cr, Ti, and indium. These conductive fillers are preferably included, and can be used alone, as an alloy, or as a mixed powder. Moreover, the electroconductive particle which coat
- the volume average particle diameter of the conductive filler (C) is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 6 ⁇ m.
- the volume average particle diameter is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 6 ⁇ m.
- the contact probability between the conductive fillers is improved, the specific resistance value of the conductive pattern to be produced, and the disconnection probability can be lowered, and the ultraviolet rays at the time of exposure are in the film. Can be transmitted smoothly, and fine patterning becomes easy.
- the volume average particle size is 10 ⁇ m or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the printed circuit pattern are improved.
- the volume average particle diameter can be determined by a Coulter counter method.
- the amount of the conductive filler (C) added is preferably in the range of 70 to 95% by weight, more preferably 80 to 90% by weight, based on the total solid content in the photosensitive conductive paste.
- 70 weight% or more especially the contact probability of the conductive fillers in the curing shrinkage at the time of curing can be improved, and the specific resistance value and the disconnection probability of the produced conductive pattern can be lowered.
- 95 weight% or less especially the ultraviolet-ray at the time of exposure can permeate
- the dicarboxylic acid or acid anhydride (D) dicarboxylic acid compound contained in the photosensitive conductive paste of the present invention is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid , Sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, 2-methylmalonic acid, 2-ethylmalonic acid, 2-propylmalonic acid, 2-butylmalonic acid, 2- (3-methoxypropyl) malonic acid, 2- (3-propoxypropyl) malonic acid, 2- (3-propoxybutyl) malonic acid, (E) -2- (hex-4-ethyl) malonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2- Propylsuccinic acid, 2-butylsuccinic acid, 2- (3-methoxypropyl) succinic acid, 2- (3-propoxyprop
- the addition amount of the dicarboxylic acid or its acid anhydride (D) is preferably in the range of 0.5 to 30 parts by weight, more preferably 1 to 100 parts by weight of the epoxy acrylate (A) having a urethane bond. ⁇ 20 parts by weight.
- the addition amount of the dicarboxylic acid or its acid anhydride (D) is preferably in the range of 0.5 to 30 parts by weight, more preferably 1 to 100 parts by weight of the epoxy acrylate (A) having a urethane bond. ⁇ 20 parts by weight.
- the photosensitive conductive paste of the present invention may contain a solvent.
- Solvents include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, ⁇ -butyrolactone, lactic acid Examples include ethyl, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, propylene glycol monomethyl ether acetate and the like.
- a solvent can be used individually by 1 type, or 2 or more types can be mixed and used for it. The solvent may be added later for the purpose of adjusting the viscosity after preparing the paste.
- the photosensitive conductive paste of the present invention is a non-photosensitive polymer, plasticizer, leveling agent, surfactant, silane coupling agent that does not have an unsaturated double bond in the molecule as long as the desired properties are not impaired. Additives such as antifoaming agents and pigments can also be blended.
- the non-photosensitive polymer include epoxy resin, novolac resin, phenol resin, polyimide precursor, and closed ring polyimide.
- plasticizer examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like.
- leveling agent examples include a special vinyl polymer and a special acrylic polymer.
- silane coupling agents methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane Etc.
- the photosensitive conductive paste of the present invention is produced using a disperser, a kneader or the like. Specific examples of these include, but are not limited to, a three-roller, a ball mill, and a planetary ball mill.
- the paste of the present invention is applied on a substrate, heated to volatilize the solvent and dried. Thereafter, exposure is performed through a pattern formation mask, and a desired pattern is formed on the substrate through a development process. And it cures at the temperature of 100 degreeC or more and 300 degrees C or less, and produces a conductive pattern.
- the curing temperature is preferably 120 to 180 ° C. If the heating temperature is less than 100 ° C., the volume shrinkage of the resin cannot be increased, and the specific resistivity cannot be decreased. On the other hand, when the heating temperature exceeds 300 ° C., it cannot be used on a substrate having low heat resistance, and cannot be used in combination with a material having low heat resistance.
- the substrate used in the present invention is, for example, 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, or glass.
- PET film polyethylene terephthalate film
- a polyimide film a polyimide film
- polyester film an aramid film
- an epoxy resin substrate a polyetherimide resin substrate
- a polyetherketone resin substrate a polysulfone resin substrate
- glass glass
- examples include, but are not limited to, a substrate, a decorative layer forming substrate, an insulating layer forming substrate, a silicon wafer, an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate.
- Examples of the method for applying the photosensitive conductive paste of the present invention to a substrate include spin coating using a spinner, spray coating, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater and the like.
- the coating film thickness varies depending on the coating method, the total solid content concentration of the composition, the viscosity, and the like, but is usually applied such that the film thickness after drying is in the range of 0.1 to 50 ⁇ m.
- the solvent is removed from the coating film applied on the substrate.
- the method for removing the solvent include heat drying using an oven, a hot plate, infrared rays, and vacuum drying. Heat drying is preferably performed in the range of 50 ° C. to 180 ° C. for 1 minute to several hours.
- the pattern is processed by photolithography on the coating film after removing the solvent.
- a light source used for exposure it is preferable to use i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp.
- Developer solutions for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate
- An aqueous solution of a compound such as dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine or hexamethylenediamine is preferred.
- these aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and ⁇ -butyrolactone, alcohols such as methanol, ethanol and isopropanol.
- polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and ⁇ -butyrolactone
- alcohols such as methanol, ethanol and isopropanol.
- Esters such as ethyl lactate and propylene glycol monomethyl ether acetate
- ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be used alone or as a developer.
- what added surfactant to these alkaline aqueous solution can also be
- Developers for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethyl phosphortriamide, etc. Can be used alone or in combination with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, ethyl carbitol and the like.
- the development can be performed by spraying the developer on the coating film surface while the substrate is allowed to stand or rotate, immersing the substrate in the developer, or applying ultrasonic waves while immersing.
- a rinsing treatment with water may be performed.
- alcohols such as ethanol and isopropyl alcohol
- esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
- the paste composition film is cured to develop conductivity.
- the curing method include oven drying, inert oven, hot plate, heat drying using infrared rays, vacuum drying, and the like.
- a conductive pattern can be produced through a curing process.
- the conductive pattern manufactured using the photosensitive conductive paste of the present invention is suitably used as a peripheral wiring for a touch panel.
- Examples of 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.
- the conductive pattern manufactured using is more preferably used.
- One unit is a group of straight lines in which a photosensitive conductive paste is applied on a PET film to a dry thickness of 7 ⁇ m, dried in a drying oven at 100 ° C. for 5 minutes, and arranged in a constant line and space (L / S). And exposing and developing through a photomask having a light-transmitting pattern having nine types of units having different L / S values, and then curing in a drying oven at 140 ° C. for 30 minutes to obtain a conductive pattern .
- the L / S values of each unit were 500/500, 250/250, 100/100, 50/50, 40/40, 30/30, 25/25, 20/20, and 15/15 (respective line widths).
- Specific resistivity surface resistance value ⁇ film thickness ⁇ line width / line length
- the film thickness was measured using a stylus type step gauge Surfcom (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). The film thickness was measured at three positions at random, and the average value of the three points was taken as the film thickness. The length measurement was 1 mm, and the scanning speed was 0.3 mm / sec.
- the line width was determined by observing three positions at random with an optical microscope and analyzing the image data to obtain the average value of the three points as the line width.
- FIG. 2 is a diagram schematically showing a sample used in the flexibility test.
- a photosensitive conductive paste is applied to a rectangular PET film (thickness 40 ⁇ m) having a length of 10 mm and a width of 100 mm so as to have a dry thickness of 7 ⁇ m, followed by drying in a drying oven at 100 ° C. for 5 minutes.
- a photomask having a translucent portion A is arranged so that the translucent portion is at the center of the sample, exposed, developed, and then cured in a drying oven at 140 ° C. for 30 minutes to form a conductive pattern.
- the conductive pattern was bent so that the inner side and the outer side were alternately bent, the sample short side B and the sample short side C were brought into contact, and the bending operation to return to the original was repeated 100 times, and then the resistance value was measured again with a tester.
- the change amount of the resistance value was 20% or less and the conductive pattern was not cracked, peeled off, disconnected, or the like.
- the photosensitive conductive paste was applied on a PET film ELECRYSTA (registered trademark) V270L-TFS (manufactured by Nitto Denko Corporation) with ITO so that the dry thickness was 7 ⁇ m, and dried in a drying oven at 100 ° C. for 5 minutes. The entire printed surface is exposed, then cured in a drying oven at 140 ° C. for 30 minutes, then cut into a 1 ⁇ 10 10 ⁇ 10 grid pattern with a cutter, and a constant temperature and humidity chamber at 85 ° C. and 85% RH The mixture was put into SH-661 (Espec Corp.) for 240 hours. Thereafter, the sample was taken out, and the tape was attached to a grid-like portion and peeled off. As the tape, cellophane tape (manufactured by Nichiban Co., Ltd.) was used.
- SH-661 Espec Corp.
- Synthesis Example A-2 200 g of epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 476.7, having bisphenol A skeleton) as epoxy acrylate compound (a) in reaction vessel, 500 g of diethylene glycol monoethyl ether acetate as reaction solvent, thermal polymerization inhibitor As a diol compound, 0.5 g of 2-methylhydroquinone and 100 g of 1,6-hexanediol (molecular weight: 118.2) were added, and the temperature was raised to 45 ° C.
- Synthesis Example A-3 200 g of epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 476.7, having bisphenol A skeleton) as epoxy acrylate compound (a) in reaction vessel, 500 g of diethylene glycol monoethyl ether acetate as reaction solvent, thermal polymerization inhibitor As a diol compound, 0.5 g of 2-methylhydroquinone and 10 g of 1,4-benzenediol (molecular weight: 110.1) were added, and the temperature was raised to 45 ° C.
- Synthesis Example A-4 200 g of epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 476.7, having bisphenol A skeleton) as epoxy acrylate compound (a) in reaction vessel, 500 g of diethylene glycol monoethyl ether acetate as reaction solvent, thermal polymerization inhibitor As a diol compound, 0.5 g of 2-methylhydroquinone and 20 g of dihydroxypropionic acid (molecular weight: 106.1) were added, and the temperature was raised to 45 ° C.
- naphthalene-1,5-diisocyanate (molecular weight: 210.2) was added as a diisocyanate compound (b), and the solution was gradually added dropwise so that the reaction temperature did not exceed 50 ° C. After completion of the dropwise addition, the temperature was raised to 80 ° C., and the reaction was continued for 6 hours until absorption near 2250 cm ⁇ 1 disappeared by infrared absorption spectrum measurement.
- a photosensitive resin solution of 34.5% by weight of epoxy acrylate (A-4) containing a urethane bond of the present invention was obtained.
- the acid value of the obtained compound (A-4) was 35 mgKOH / g, and the glass transition temperature obtained from DSC measurement was 66.2 ° C.
- Synthesis Example A-5 200 g of epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 476.7, having bisphenol A skeleton) as epoxy acrylate compound (a) in reaction vessel, 500 g of diethylene glycol monoethyl ether acetate as reaction solvent, thermal polymerization inhibitor As a diol compound, 0.5 g of 2-methylhydroquinone and 75 g of dihydroxypropionic acid (molecular weight: 106.1) were added, and the temperature was raised to 45 ° C.
- An epoxy acrylate (A-6) having 59.9% by weight of a photosensitive resin solution was obtained.
- the acid value of the obtained compound (A-6) was 78 mgKOH / g, and the glass transition temperature obtained from DSC measurement was 15.1 ° C.
- Synthesis Example A-7 Epoxylite 4000 (manufactured by Kyoeisha Chemical Co., Ltd., molecular weight: 332.4, having hydrogenated bisphenol A skeleton) as an epoxy acrylate compound (a) in a reaction vessel, 300 g of acrylic acid adduct (molecular weight: 496.5), for reaction Add 500 g of diethylene glycol monoethyl ether acetate as a solvent, 0.5 g of 2-methylhydroquinone as a thermal polymerization inhibitor, and 120 g of 2,2-bis (hydroxymethyl) propionic acid (molecular weight: 134.1) as a diol compound having a carboxyl group The temperature was raised to 45 ° C.
- An epoxy acrylate (A-7) having 58.1% by weight of a photosensitive resin solution was obtained.
- the acid value of the obtained compound (A-7) was 102 mgKOH / g, and the glass transition temperature obtained from DSC measurement was 23.4 ° C.
- Synthesis Example A-8 Denacol EX-203 (manufactured by Nagase ChemteX Corp., molecular weight: 224, having no bisphenol A skeleton, bisphenol F skeleton, biphenyl skeleton, or hydrogenated bisphenol A skeleton) as an epoxy acrylate compound (a) in the reaction vessel 300 g of acrylic acid adduct (molecular weight: 368), 500 g of diethylene glycol monoethyl ether acetate as a reaction solvent, 0.5 g of 2-methylhydroquinone as a thermal polymerization inhibitor, 2,2-bis (hydroxy) as a diol compound having a carboxyl group 200 g of methyl) propionic acid (molecular weight: 134.1) was added and the temperature was raised to 45 ° C.
- Denacol EX-203 manufactured by Nagase ChemteX Corp., molecular weight: 224, having no bisphenol A skeleton, bisphenol F skeleton, bipheny
- An epoxy acrylate (A-8) having a photosensitive resin solution of 62.2% by weight was obtained.
- the acid value of the obtained compound (A-8) was 83 mgKOH / g, and the glass transition temperature obtained from DSC measurement was 12.4 ° C.
- volume average particle size of the conductive filler (C) was measured with a dynamic light scattering particle size distribution meter manufactured by Horiba, Ltd.
- the obtained paste was applied on a PET film having a thickness of 100 ⁇ m by screen printing, and dried in a drying oven at 90 ° C. for 10 minutes. Then, full exposure was performed using an exposure apparatus PEM-6M (manufactured by Union Optics Co., Ltd.) with an exposure amount of 150 mJ / cm 2 (wavelength 365 nm conversion), and immersion development was performed with a 0.25% Na 2 CO 3 solution for 30 seconds. After rinsing with ultrapure water, curing was performed in a drying oven at 140 ° C. for 30 minutes. The film thickness of the patterned conductive pattern was 7 ⁇ m.
- 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 shown in Table 2.
- Examples 1 to 18 that satisfy the requirements of the present invention, a high-resolution pattern could be formed, and a low-resistance conductive pattern could be obtained by curing at 140 ° C., but the comparison without using the photosensitive component (A) In Examples 1 to 4, adhesion with ITO decreased under high temperature and high humidity.
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Abstract
Description
また、ウレタン結合とカルボキシル基を有するエポキシアクリレート(A)に不飽和二重結合を有するエポキシ化合物(d)を反応させることで不飽和二重結合を有する化合物(A)を得ることができる。
本発明の感光性導電ペーストに含まれる導電フィラー(C)はAg、Au、Cu、Pt、Pb、Sn、Ni、Al、W、Mo、酸化ルテニウム、Cr、Ti、およびインジウムの少なくとも1種を含むことが好ましく、これらの導電フィラーを単独、合金、あるいは混合粉末として用いることができる。また、上述の成分で絶縁性粒子または導電性粒子の表面を被膜した導電性粒子も同様に用いることができる。中でも導電性の観点からAg、CuおよびAuが好ましく、コスト、安定性の観点からAgがより好ましい。
PETフィルム上に感光性導電ペーストを乾燥厚みが7μmになるように塗布、100℃の乾燥オーブン内で5分間乾燥し、一定のラインアンドスペース(L/S)で配列する直線群を1つのユニットとし、L/Sの値が異なる9種類のユニットを有する透光パターンを有するフォトマスクを介して露光、現像し、その後、140℃で30分間乾燥オーブン内でキュアすることによって導電パターンを得た。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とした(それぞれライン幅(μm)/間隔(μm)を表す)。パターンを光学顕微鏡により観察し、パターン間に残渣がなく、かつパターン剥がれのない最小のL/Sの値を持つパターンを確認し、この最小のL/Sの値を現像可能なL/Sとした。
100℃の乾燥オーブン内で5分間乾燥し、図1に示すパターンの透光部Aを有するフォトマスクを介して露光し、現像し、その後、140℃で30分間乾燥オーブン内でキュアすることによって比抵抗率測定用導電性パターンを得た。導電性パターンのライン幅は0.400mm、ライン長さは80mmである。得られたパターンの端部を表面抵抗計でつなぎ、表面抵抗値を測定し、次の計算式に当てはめて比抵抗率を算出した。
比抵抗率=表面抵抗値×膜厚×線幅/ライン長
なお膜厚の測定は触針式段差計サーフコム(登録商標)1400((株)東京精密製)を用いて行った。膜厚の測定はランダムに3箇所の位置にて測り、その3点の平均値を膜厚とした。測長は1mm、走査速度は0.3mm/secとした。線幅はパターンを光学顕微鏡でランダムに3箇所の位置を観察し、画像データを解析して得られた3点の平均値を線幅とした。
図2は屈曲性試験に用いたサンプルを模式的に示した図である。縦10mm、横100mmの長方形のPETフィルム(厚み40μm)上に感光性導電ペーストを乾燥厚みが7μmになるように塗布し、100℃の乾燥オーブン内で5分間乾燥し、図1に示すパターンの透光部Aを有するフォトマスクを、透光部がサンプル中央になるように配置して露光し、現像し、その後、140℃で30分間乾燥オーブン内でキュアして導電パターンを形成し、テスターを用いて抵抗値を測定した。その後導電パターンが内側、外側と交互になるように曲げてサンプル短辺Bとサンプル短辺Cを接触させ、元に戻す屈曲動作を100回繰り返した後、再度テスターで抵抗値を測定した。その結果、抵抗値の変化量が20%以下であり、且つ導電パターンにクラック、剥がれ、断線などがないものをgoodとし、そうでないものをpoorとした。
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厚みが7μmになるように塗布し、100℃の乾燥オーブン内で5分間乾燥し、印刷面を全面露光し、その後、140℃で30分間乾燥オーブン内でキュアした後、1mm幅で10×10の碁盤目状にカッターで切れ目を入れ、85℃、85%RHの恒温恒湿槽SH-661(エスペック(株)製)に240h投入した。その後サンプルを取り出し、碁盤目状の箇所にテープを貼着して剥がし、残存マス数で判定を行った。なお、テープとしてはセロハンテープ(ニチバン(株)製)を用いて行った。
合成例A-1:
反応容器にエポキシアクリレート化号物(a)としてエポキシエステル3000A(共栄社化学(株)製、分子量:476.7、ビスフェノールA骨格を有する)200g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、カルボキシル基を有するジオール化合物としてジヒドロキシプロピオン酸(分子量:106.1)75g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてヘキサメチレンジイソシアネート(分子量:168.2)84.1g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させた。この溶液に分子中に不飽和二重結合を有するエポキシ化合物(d)としてグリシジルメタクリレート(分子量:142.2)165g添加後、95℃に昇温し、6時間反応させて本発明のウレタン結合を含むエポキシアクリレート(A-1)51.2重量%の感光性樹脂溶液を得た。得られた化合物(A-5)の酸価は89mgKOH/g、DSC測定から得られたガラス転移温度は27.2℃であった。
反応容器にエポキシアクリレート化合物(a)としてエポキシエステル3000A(共栄社化学(株)製、分子量:476.7、ビスフェノールA骨格を有する)200g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、ジオール化合物として1,6-ヘキサンジオール(分子量:118.2)100g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてヘキサメチレンジイソシアネート(分子量:168.2)71.0g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させて、本発明のウレタン結合を含むエポキシアクリレート(A-2)42.6重量%の感光性樹脂溶液を得た。得られた化合物(A-2)の酸価は1mgKOH/g以下、DSC測定から得られたガラス転移温度は35.5℃であった。
反応容器にエポキシアクリレート化合物(a)としてエポキシエステル3000A(共栄社化学(株)製、分子量:476.7、ビスフェノールA骨格を有する)200g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、ジオール化合物として1,4-ベンゼンジオール(分子量:110.1)10g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてヘキサメチレンジイソシアネート(分子量:168.2)28.6g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させて、本発明のウレタン結合を含むエポキシアクリレート(A-3)32.4重量%の感光性樹脂溶液を得た。得られた化合物(A-3)の酸価は1mgKOH/g以下、DSC測定から得られたガラス転移温度は79.3℃であった。
反応容器にエポキシアクリレート化合物(a)としてエポキシエステル3000A(共栄社化学(株)製、分子量:476.7、ビスフェノールA骨格を有する)200g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、ジオール化合物としてジヒドロキシプロピオン酸(分子量:106.1)20g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてナフタレン-1,5-ジイソシアネート(分子量:210.2)42.6g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させた。本発明のウレタン結合を含むエポキシアクリレート(A-4)34.5重量%の感光性樹脂溶液を得た。得られた化合物(A-4)の酸価は35mgKOH/g、DSC測定から得られたガラス転移温度は66.2℃であった。
反応容器にエポキシアクリレート化合物(a)としてエポキシエステル3000A(共栄社化学(株)製、分子量:476.7、ビスフェノールA骨格を有する)200g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、ジオール化合物としてジヒドロキシプロピオン酸(分子量:106.1)75g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてヘキサメチレンジイソシアネート(分子量:168.2)62.8g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させた。本発明のウレタン結合を含むエポキシアクリレート(A-5)40.4重量%の感光性樹脂溶液を得た。得られた化合物(A-5)の酸価は112mgKOH/g、DSC測定から得られたガラス転移温度は25.4℃であった。
反応容器にエポキシアクリレート化合物(a)としてエポキシエステル70PA(共栄社化学(株)製、分子量:332.4、ビスフェノールA骨格、ビスフェノールF骨格、ビフェニル骨格、または水添ビスフェノールA骨格を有さない)350g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、カルボキシル基を有するジオール化合物としてジヒドロキシプロピオン酸(分子量:106.1)80g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてヘキサメチレンジイソシアネート(分子量:168.2)121.1g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させた。この溶液に分子中に不飽和二重結合を有するエポキシ化合物(d)としてグリシジルメタクリレート(分子量:142.2)195g添加後、95℃に昇温し、6時間反応させて本発明のウレタン結合を有するエポキシアクリレート(A-6)59.9重量%の感光性樹脂溶液を得た。得られた化合物(A-6)の酸価は78mgKOH/g、DSC測定から得られたガラス転移温度は15.1℃であった。
反応容器にエポキシアクリレート化合物(a)としてエポライト4000(共栄社化学(株)製、分子量:332.4、水添ビスフェノールA骨格を有する)のアクリル酸付加物(分子量:496.5)300g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、カルボキシル基を有するジオール化合物として2,2-ビス(ヒドロキシメチル)プロピオン酸(分子量:134.1)120g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてトルエンジイソシアネート(分子量:174.2)104.2g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させた。この溶液に分子中に不飽和二重結合を有するエポキシ化合物(d)としてグリシジルメタクリレート(分子量:142.2)170g添加後、95℃に昇温し、6時間反応させて本発明のウレタン結合を有するエポキシアクリレート(A-7)58.1重量%の感光性樹脂溶液を得た。得られた化合物(A-7)の酸価は102mgKOH/g、DSC測定から得られたガラス転移温度は23.4℃であった。
反応容器にエポキシアクリレート化合物(a)としてデナコールEX-203(ナガセケムテックス(株)製、分子量:224、ビスフェノールA骨格、ビスフェノールF骨格、ビフェニル骨格、または水添ビスフェノールA骨格を有さない)のアクリル酸付加物(分子量:368)300g、反応用溶媒としてジエチレングリコールモノエチルエーテルアセテート500g、熱重合禁止剤として2-メチルハイドロキノンを0.5g、カルボキシル基を有するジオール化合物として2,2-ビス(ヒドロキシメチル)プロピオン酸(分子量:134.1)200g加え、45℃に昇温させた。この溶液にジイソシアネート化合物(b)としてトルエンジイソシアネート(分子量:174.2)201.3g加え、反応温度が50℃を超えないように徐々に滴下した。滴下終了後、温度を80℃に上昇させ、赤外吸収スペクトル測定法により、2250cm-1付近の吸収がなくなるまで6時間反応させた。この溶液に分子中に不飽和二重結合を有するエポキシ化合物(d)としてグリシジルメタクリレート(分子量:142.2)120g添加後、95℃に昇温し、6時間反応させて本発明のウレタン結合を有するエポキシアクリレート(A-8)62.2重量%の感光性樹脂溶液を得た。得られた化合物(A-8)の酸価は83mgKOH/g、DSC測定から得られたガラス転移温度は12.4℃であった。
IRGACURE(登録商標)369(チバジャパン(株)製)
[導電フィラー(C)]
表1に記載の材料、体積平均粒子径のものを用いた。なお、体積平均粒子径は以下の方法により求めた。
導電フィラー(C)の体積平均粒子径は、(株)堀場製作所製動的光散乱式粒度分布計により体積平均粒子径を測定した。
2-プロピルサクシン酸(東京化成工業(株)製)
2-ヘキシルマロン酸(東京化成工業(株)製)
[モノマー]
ライトアクリレートBP-4EA(共栄社化学(株)製)
EBECRYL770(ダイセル・サイテック(株)製;酸価:120mgKOH/g)
[溶剤]
ジエチレングリコールモノエチルエーテルアセテート(東京化成工業(株)製)
[ウレタン結合を含まないエポキシアクリレート]
エポキシエステル3002M(共栄社化学(株)製、ビスフェノールA骨格を有する)
ネオポール(登録商標)8317(ユピカ(株)製;臭素化ビスフェノールA骨格を有する、酸価:110mgKOH/g)
ネオポール(登録商標)8475(ユピカ(株)製;ビスフェノールF骨格を有する、酸価:55mgKOH/g)
(実施例1)
100mLクリーンボトルに感光性樹脂溶液(A-1)を10.0g、光重合開始剤IRGACURE(登録商標)369(チバジャパン(株)製)を1.0g“あわとり錬太郎”(登録商標)ARE-310((株)シンキー製)で混合し、感光性樹脂溶液11.0g(全固形分55.6重量%)を得た。
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、評価結果を表2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、評価結果を表2に示した。
B、C:サンプル短辺
D:導電パターン
E:PETフィルム
Claims (9)
- ウレタン結合を有するエポキシアクリレート(A)、光重合開始剤(B)、および導電フィラー(C)を含む感光性導電ペースト。
- 前記ウレタン結合を有するエポキシアクリレート(A)がカルボキシル基を有する請求項1記載の感光性導電ペースト。
- 前記ウレタン結合を有するエポキシアクリレート(A)の酸価が40~250mgKOH/gの範囲内である請求項1または2記載の感光性導電ペースト。
- 前記ウレタン結合を有するエポキシアクリレート(A)が不飽和二重結合を含む請求項1~3のいずれかに記載の感光性導電ペースト。
- 前記ウレタン結合を有するエポキシアクリレート(A)がビスフェノールA骨格、ビスフェノールF骨格、ビフェニル骨格、または水添ビスフェノールA骨格を有する請求項1~4のいずれかに記載の感光性導電ペースト。
- 前記ウレタン結合を有するエポキシアクリレート(A)のガラス転移温度が-10~60℃の範囲内である請求項1~5のいずれかに記載の感光性導電ペースト。
- さらにジカルボン酸またはその酸無水物(D)を含む請求項1~6のいずれかに記載の感光性導電ペースト。
- 請求項1~7のいずれかに記載の感光性導電ペーストを基板上に塗布し、乾燥し、露光し、現像した後に100℃以上300℃以下の温度でキュアする導電パターンの製造方法。
- 請求項8記載の導電パターンを備えるタッチパネル。
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WO2016170943A1 (ja) * | 2015-04-21 | 2016-10-27 | 東レ株式会社 | 積層部材及びタッチパネル |
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TW201348354A (zh) | 2013-12-01 |
TWI565768B (zh) | 2017-01-11 |
JP5928453B2 (ja) | 2016-06-01 |
JPWO2013146107A1 (ja) | 2015-12-10 |
US20150056560A1 (en) | 2015-02-26 |
KR20140148400A (ko) | 2014-12-31 |
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