WO2011114846A1 - 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 PDF

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Publication number
WO2011114846A1
WO2011114846A1 PCT/JP2011/053943 JP2011053943W WO2011114846A1 WO 2011114846 A1 WO2011114846 A1 WO 2011114846A1 JP 2011053943 W JP2011053943 W JP 2011053943W WO 2011114846 A1 WO2011114846 A1 WO 2011114846A1
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Prior art keywords
photosensitive
conductive paste
glass transition
transition temperature
photosensitive conductive
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PCT/JP2011/053943
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English (en)
French (fr)
Japanese (ja)
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水口創
草野一孝
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東レ株式会社
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Priority to CN201180014597XA priority Critical patent/CN102812399A/zh
Priority to JP2011509744A priority patent/JPWO2011114846A1/ja
Priority to KR1020127018020A priority patent/KR20130016192A/ko
Publication of WO2011114846A1 publication Critical patent/WO2011114846A1/ja

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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • 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
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a photosensitive conductive paste for forming a conductive pattern having flexibility.
  • 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.
  • an inorganic conductive pattern can be obtained by applying and drying a paste containing a resin and a conductive filler, followed by baking.
  • a high temperature of 500 ° C. or higher it is provided on a substrate having low heat resistance. It has the disadvantage that it cannot.
  • the organic-inorganic composite conductive pattern can be formed by processing at a relatively low temperature, but it has been relatively difficult to achieve high conductivity.
  • a paste in which conductive fine particles are dispersed in photosensitive polyimide is applied, dried, exposed, developed, and after forming a fine pattern, the conductive fine particles are brought into contact with each other by shrinking the resin by curing.
  • a bump forming method for developing conductivity for example, see Patent Document 4
  • a method for producing a conductive pad, wiring, and the like using a photosensitive conductive paste in which silver powder is dispersed in a photosensitive phenoxy resin (For example, refer to Patent Documents 5 and 6).
  • Patent Document 3 requires a resist layer to be formed on the coating film in order to perform patterning by a photolithography method, and there is a problem that the number of steps increases.
  • patent document 4 in order to express electroconductivity, it was necessary to heat to about 400 degreeC, and there existed a subject that the base material to be used was restricted.
  • Patent Documents 5 and 6 a photosensitive phenoxy resin or a photosensitive acrylic-modified epoxy resin can be used to develop conductivity at a low temperature, but the resulting conductive pattern has a high specific resistance value and a fineness of 50 ⁇ m or less. There was a problem that patterning was difficult.
  • Patent Documents 7 and 8 a fine pattern can be formed, but in Patent Document 7, the conductivity is low, and in the method described in Patent Document 8, it is necessary to reduce the acrylic (methacrylic) equivalent in order to develop conductivity. There was a problem that the obtained conductive pattern was brittle.
  • the conductive pastes described in the cited references 1 to 8 are inferior in the flexibility of the obtained conductive pattern, and therefore when the conductive pattern is provided on a flexible substrate such as a film, peeling or disconnection occurs, resulting in a decrease in conductivity. There was a problem of doing.
  • An object of the present invention is to provide a photosensitive conductive paste that can solve the above-mentioned problems, can obtain a conductive pattern having high conductivity at a relatively low temperature, and excellent flexibility, and a conductive pattern produced using the same. It is to obtain a manufacturing method.
  • the photosensitive conductive paste of the present invention has the following configuration. That is, a compound (A) having an alkoxy group, a photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C., a photopolymerization initiator (C), and a conductive filler ( D) is a photosensitive conductive paste characterized by containing.
  • a conductive pattern having high conductivity at a relatively low temperature and excellent flexibility can be easily formed.
  • the photosensitive conductive paste of the present invention comprises a compound (A) having an alkoxy group, a photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C., a photopolymerization initiator (C)
  • a conductive filler (D) is dispersed in a photosensitive resin obtained by mixing the above.
  • the paste is a photosensitive conductive paste that can be applied on a substrate, dried to remove the solvent, and then a desired conductive pattern can be obtained on the substrate through exposure, development, and curing steps.
  • the obtained conductive pattern is an organic-inorganic composite, and the conductive fillers are brought into contact with each other by curing shrinkage during curing, so that conductivity is exhibited.
  • the compound (A) having an alkoxy group contained in the photosensitive conductive paste of the present invention is a compound having in its molecule an alkoxy group that generates an alcohol by heating to condense.
  • the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, an isobutoxy group, and the like.
  • the molecular weight of the alcohol generated during the condensation is relatively large.
  • a butoxy group, an isobutoxy group, and the like are preferable, and at least one butoxy group is present. More preferably.
  • Such a compound (A) include N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, Nn-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, butoxyethyl acrylate, butoxytriethylene glycol acrylate, Honshu HMOM-TPHAP manufactured by Chemical Industry Co., Ltd., alkylated amino compounds manufactured by Sanwa Chemical Co., Ltd., MW-30M, MW-30, MW-22, MS-11, MS-001, MX-730, MX-750, MX- 706, MX-035, BL-60, BX-37, MX-302, MX-45, MX-410, BX-4000, BX-37, Nikarak MW-30HM, Nikarak MW-390, Nikarak MX-270, Nikarak MX-280, Nikarak MW-10 LM, and the like NIKALACK MX-750LM.
  • Nicarak is a registered trademark.
  • the addition amount of the compound (A) having an alkoxy group contained in the photosensitive conductive paste of the present invention has an unsaturated double bond and a glass transition temperature (hereinafter referred to as Tg) of 5 to 40 ° C.
  • the amount is preferably 10 to 300 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the photosensitive component (B).
  • the amount of shrinkage during curing is particularly increased by adding 50 parts by weight or more with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and having a Tg in the range of 5 to 40 ° C.
  • the contact probability between the conductive fillers can be increased. As a result, the specific resistivity of the conductive pattern that is the final composition can be lowered.
  • the paste after removing the solvent in particular The tackiness of the composition film can be reduced, and the occurrence of defects in the conductive pattern can be suppressed.
  • the photosensitive component (B) having an unsaturated double bond used in the present invention and having a Tg in the range of 5 to 40 ° C. is a monomer, oligomer or oligomer having at least one unsaturated double bond in the molecule. It refers to a polymer and can be used alone or in combination of two or more.
  • the photosensitive component (B) is not particularly limited, it is preferable to include an alkali-soluble polymer because development with the pattern processing of the present invention is preferably performed with an aqueous alkali solution instead of an organic solvent.
  • alkali-soluble polymer examples include acrylic copolymers.
  • the acrylic copolymer is a copolymer containing at least an acrylic monomer as a copolymerization component, and as a specific example of the acrylic monomer, all compounds having a carbon-carbon double bond can be used.
  • methyl acrylate acrylic acid, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl acrylate, i-butyl acrylate, i-propane acrylate, glycidyl acrylate, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N- n-butoxymethylacrylamide, N-isobutoxymethylacrylamide, butoxytriethylene glycol acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl acrylate, isobonyl acrylate Relate, 2-hydroxypropyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, methoxydiethylene glycol acrylate, octafluoropentyl acrylate, phen
  • the glass transition temperature of the photosensitive component (B) having an unsaturated double bond used in the present invention and having a Tg in the range of 5 to 40 ° C. is measured by a differential scanning calorimeter (DSC) of the photosensitive component.
  • DSC differential scanning calorimeter
  • Tg is the glass transition temperature of the polymer (unit: K)
  • T1, T2, T3... Are the glass transition temperatures of the homopolymer of monomer 1, monomer 2, monomer 3,.
  • W2, W3,... Are the weight-based copolymerization ratios of monomer 1, monomer 2, monomer 3,.
  • the photosensitive component (B) having an unsaturated double bond used in the present invention and having a Tg in the range of 5 to 40 ° C. needs to have a glass transition temperature of 5 to 40 ° C. 30 is preferable.
  • Tg is 5 ° 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. Further, when Tg is 40 ° C. or lower, flexibility is exhibited at room temperature, and when it is 30 ° C. or lower, internal stress at the time of bending can be relaxed, and generation of cracks can be particularly suppressed.
  • the acid value of the photosensitive component (B) having an unsaturated double bond used in the present invention and having a Tg in the range of 5 to 40 ° C. is 50 to 200 mg KOH / g from the viewpoint of development with an aqueous alkaline solution. It is preferably 80 to 150 mgKOH / g. When the acid value is 80 mgKOH / g or more, the solubility of the soluble part in the developer does not decrease, and when the acid value is 150 mgKOH / g or less, the development tolerance can be widened.
  • the acid value is measured according to JIS-K0070 (1992).
  • the photopolymerization initiator (C) contained in the photosensitive conductive paste of the present invention refers to a compound that absorbs light of a short wavelength such as ultraviolet rays and decomposes to generate radicals.
  • a short wavelength such as ultraviolet rays and decomposes to generate radicals.
  • Specific 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 (
  • the addition amount of the photopolymerization initiator (C) is preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C. It is added in the range of 30 parts by weight, and more preferably 5 to 20 parts by weight.
  • the addition amount of the photopolymerization initiator (C) 5 parts by weight or more with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C.
  • the cured density of the exposed area is increased, and the remaining film ratio after development can be increased.
  • the photopolymerization initiator (C) by adding 20 parts by weight or less of the photopolymerization initiator (C) to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and having a glass transition temperature of 5 to 40 ° C.
  • the photosensitive component (B) having an unsaturated double bond and having a glass transition temperature of 5 to 40 ° C.
  • a sensitizer can be added together with the photopolymerization initiator (C) to improve sensitivity, or the wavelength range effective for the reaction can be expanded.
  • 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 amount added is 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C.
  • the amount added is 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C.
  • it is preferably in the range of 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight.
  • the effect of improving the photosensitivity is sufficient by adding 0.1 parts by weight or more with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C.
  • the photosensitive component (B) By adding 10 parts by weight or less to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and having a glass transition temperature of 5 to 40 ° C. Excessive light absorption occurs in the conductive pattern, the conductive pattern becomes a reverse taper shape, and the adhesiveness with the substrate can be prevented from being lowered.
  • the conductive filler (D) contained in the photosensitive conductive paste of the present invention is at least one of Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, ruthenium oxide, Cr, Ti, and indium.
  • These conductive fillers can be used alone, as an alloy, or as a mixed powder.
  • covered the surface of the insulating particle or electroconductive particle with the above-mentioned component can be used similarly.
  • Ag, Cu and Au are preferable from the viewpoint of conductivity, and Ag is more preferable from the viewpoint of cost and stability.
  • the average particle diameter of the conductive filler (D) is preferably 0.5 to 10 ⁇ m, more preferably 1 to 6 ⁇ m.
  • the average particle size is 1 ⁇ m or more, 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 smoothly in the film And fine patterning becomes easy.
  • the average particle size is 6 ⁇ m or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the printed circuit pattern are improved.
  • the average particle diameter can be determined by a Coulter counter method, a photon correlation method, a laser diffraction method, or the like.
  • the amount of the conductive filler (D) 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.
  • 80 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.
  • by setting it to 90% by weight or less particularly ultraviolet rays at the time of exposure can smoothly pass through the film, and fine patterning becomes easy.
  • the solid content is obtained by removing the solvent from the photosensitive conductive paste.
  • the acid generator (E) contained in the photosensitive conductive paste of the present invention refers to a substance that reacts with light or heat to generate an acid. Due to the catalytic effect of the acid generated, it has the effect of accelerating the condensation reaction of the alkoxy group in the compound (A) having an alkoxy group at a low temperature. As a result, it is possible to develop conductivity under a lower temperature curing condition and reduce the specific resistivity.
  • photoacid generators examples include quinonediazide, diazodisulfone, and triphenylsulfonium substances
  • thermal acid generators examples include sulfonium salts. Since the photoacid generator generates an acid in the exposed portion by exposure, a difference in solubility between the exposed portion and the unexposed portion is reduced, and there is a possibility that the patterning property may be adversely affected. From the viewpoint of acid strength, a sulfonium salt is more preferable.
  • the amount of the acid generator (E) added is 0.01 to 5 parts by weight with respect to 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C. It is preferably within the range, more preferably 0.05 to 5 parts by weight.
  • the compound (F) having a total chlorine content of 300 ppm or more contained in the photosensitive conductive paste of the present invention is not particularly limited as long as the total chlorine content contained in the compound is 300 rpm or more.
  • the total chlorine amount refers to the total content of chlorine ions and chlorine atoms contained in the compound, and is present alone or incorporated in the structure, or in any form. It doesn't matter if they are. Moreover, the origin of these chlorine ions and chlorine atoms is not particularly limited.
  • Examples of the compound (F) having a total chlorine content of 300 ppm or more include a glycidyl group-containing compound that is an epichlorohydrin-derived compound, an unsaturated double bond adduct thereof, and the like.
  • Specific examples of the glycidyl group-containing compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, hydrogenated bisphenol type.
  • Epoxy resin bisphenol fluorene type epoxy resin, biscresol fluorene type epoxy resin, bisphenoxyethanol fluorene type epoxy resin, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether , Trimethylolpropane polyglycidyl ether, resorcinol diglycy Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Ether, allyl glycidyl ether,
  • the addition amount of the compound (F) having a total chlorine content of 300 ppm or more is preferably based on 100 parts by weight of the photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C. Is added in the range of 0.05 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight.
  • the final composition The conductivity of the product can be increased, and by adjusting the amount of the compound (F) to be 30 parts by weight or less, the development margin and the adhesiveness under high temperature and high humidity can be improved.
  • the total chlorine content in the total solid content excluding the conductive filler (D) of the photosensitive conductive paste of the present invention is preferably 100 ppm or more because the conductivity of the final composition can be increased.
  • the total chlorine content in the total solid content excluding the compound (F) and the conductive filler (D) of the photosensitive conductive paste of the present invention can be measured using a chlorine analyzer.
  • the compound (F) diluted 100-fold with a solvent is used as a measurement sample, the photosensitive conductive paste of the present invention is centrifuged, the obtained supernatant solution is dried, and the obtained organic component is again used as a solvent.
  • a sample diluted 100 times with was used as a measurement sample.
  • membrane of the photosensitive electrically conductive paste was performed, and it computed using the weight decreasing rate.
  • the photosensitive conductive paste of the present invention may contain a solvent.
  • the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, ⁇ -butyrolactone, ethyl lactate, 1-methoxy-2-propanol, 1 -Ethoxy-2-propanol, ethylene glycol mono-n-propyl ether, diacetone alcohol, tetrahydrofurfuryl alcohol, 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 electrically conductive paste of this invention is produced using a disperser, a kneader, etc. Specific examples of these include, but are not limited to, a three-roller, a ball mill, and a planetary ball mill.
  • a disperser a kneader
  • specific examples of these include, but are not limited to, a three-roller, a ball mill, and a planetary ball mill.
  • the manufacturing method of the conductive pattern using the photosensitive electrically conductive paste of this invention is demonstrated.
  • 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 and produces a conductive pattern.
  • Examples of the substrate used in the present invention include a silicon wafer, a ceramic substrate, and an organic substrate.
  • the ceramic substrate include a glass substrate, an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate.
  • the resin substrate include an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, a polysulfone-based resin substrate, and a polyimide.
  • a film, a polyester film, an aramid film, etc. are mentioned, However, It is not limited to these.
  • 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 solid content concentration of the composition, the viscosity, and the like, but is usually applied so 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 in order to perform a condensation reaction of the alkoxy group in the compound (A) having an alkoxy group.
  • the curing method include oven drying, inert oven, hot plate, heat drying using infrared rays, vacuum drying, and the like.
  • the curing temperature is preferably in the range of 130 to 400 ° C, more preferably 150 to 400 ° C. By setting the curing temperature to 150 ° C. or higher, the reaction rate of the condensation reaction of the compound (A) having an alkoxy group can be improved, and as a result, the contact probability between the conductive fillers is increased, and the specific resistivity is increased. Get smaller.
  • the photosensitive conductive paste of the present invention can obtain high conductivity with a relatively low temperature cure of 400 ° C. or lower, it can be used on a substrate having low heat resistance or in combination with a material having low heat resistance. it can. Thus, a conductive pattern can be produced through a curing process.
  • a photosensitive conductive paste is applied on a glass substrate so that the dry thickness is 12 ⁇ m, dried on a hot plate at 100 ° C. for 3 minutes, and a group of straight lines arranged in a constant line and space (L / S) form one unit.
  • a conductive pattern was obtained by exposure, development, and curing at 180 ° C. for 1 hour through a photomask having a light-transmitting pattern having nine types of units having different L / S values.
  • 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).
  • FIG. 2 schematically shows a sample used for the flexibility test.
  • a photosensitive conductive paste is applied onto a rectangular polyimide film (thickness 50 ⁇ m) having a length of 10 mm and a width of 100 mm so as to have a dry thickness of 10 ⁇ m, dried on a hot plate at 100 ° C. for 3 minutes, and the pattern shown in FIG.
  • a photomask having a light part A is placed and exposed so that the light-transmitting part is at the center of the sample, developed, cured in a drying oven at 180 ° C. for 1 hour to form a conductive pattern, and a resistance value using a tester Was measured.
  • 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 case where the conductive pattern was not cracked, peeled off or disconnected was marked with ⁇ , and the others were marked with x.
  • Methyl methacrylate (MMA) glass transition temperature of homopolymer: 105 ° C.
  • EA glass transition temperature of homopolymer: ⁇ 22 ° C.
  • Acrylic acid (AA) Homopolymer glass transition temperature: 106 ° C.
  • i-BA Glass transition temperature of homopolymer: -24 ° C
  • Glycidyl methacrylate (GMA) glass transition temperature of homopolymer: 74 ° C.)
  • photosensitive component B-2 was obtained by adding 5 g of glycidyl methacrylate to 25 g of methyl acrylate, 25 g of cyclomethacrylate, 30 g of isobutyl acrylate, and 15 g of acrylic acid.
  • the obtained photosensitive component B-2 had an acid value of 98 mgKOH / g and a glass transition temperature obtained from the formula (1) of 36.5 ° C.
  • photosensitive component B-3 in which 5 g of glycidyl methacrylate was added to 25 g of styrene, 25 g of cyclomethacrylate, 25 g of isobutyl acrylate, and 20 g of acrylic acid was obtained.
  • the obtained photosensitive component B-3 had an acid value of 152 mgKOH / g and a glass transition temperature of 32.7 ° C. obtained from the formula (1).
  • photosensitive component F-1 was obtained in which 5 g of glycidyl methacrylate was added to 40 g of styrene, 10 g of cyclomethacrylate, 30 g of isobutyl acrylate, and 15 g of acrylic acid.
  • the obtained photosensitive component F-1 had an acid value of 105 mgKOH / g and a glass transition temperature obtained from the formula (1) of 65.5 ° C.
  • photosensitive component F-2 in which 5 g of glycidyl methacrylate was added to 15 g of styrene, 50 g of cyclomethacrylate, 15 g of isobutyl acrylate, and 15 g of acrylic acid was obtained.
  • the obtained photosensitive component F-2 had an acid value of 100 mgKOH / g and a glass transition temperature determined by the formula (1) of ⁇ 10.2 ° C.
  • the filtrate was diluted 100 times with a solvent and filtered with a solid-phase extraction cartridge GL-PakPLS-3 (GL Science). Using the chlorine / sulfur analyzer TOX-2100H (Mitsubishi Analytech) The total chlorine content was measured.
  • the weight loss value obtained by TG measurement under the following conditions after drying the photosensitive conductive paste of the present invention at 150 ° C. for 10 hours is used. Asked.
  • TG-50 / 51H (trade name, manufactured by Shimadzu Corporation) Temperature: 600 ° C. for 1 hour Holding temperature increase rate: 5 ° C./min Atmosphere: Air / Solvent: ⁇ -Butyrolactone (Mitsubishi Gas Chemical Co., Ltd.)
  • Example 1 In a 100 ml clean bottle, 20 g of photosensitive component B-1, 12 g of Nn-butoxymethylacrylamide, 4 g of photopolymerization initiator OXE-01 (manufactured by Ciba Japan Co., Ltd.), acid generator SI-110 (Sanshin Chemical) Kogyo Co., Ltd.) (0.6 g) and ⁇ -butyrolactone (Mitsubishi Gas Chemical Co., Ltd.) (10 g) are mixed with “Awatori Nertaro” (trade name ARE-310, manufactured by Shinky Co., Ltd.).
  • the obtained paste was applied onto a polyimide film having a thickness of 50 ⁇ m by screen printing, and prebaked at 100 ° C. for 10 minutes in a drying oven. Then, full line exposure was performed using an exposure apparatus “PEM-6M” (trade name, manufactured by Union Optical Co., Ltd.) with an exposure amount of 70 mJ / cm 2 (wavelength 365 nm conversion), and 0.5% Na 2 CO 3 solution was used. Immersion development was performed for 1 minute, rinsed with ultrapure water, and then cured at 200 ° C. for 1 hour in a drying oven. The film thickness of the patterned conductive pattern was 10 ⁇ m.
  • Examples 2 to 9 A photosensitive conductive paste having the composition shown in Table 2 was produced in the same manner as in Example 1, and the evaluation results are shown in Table 3. Comparative Examples 1 to 3 A photosensitive conductive paste having the composition shown in Table 2 was produced in the same manner as in Example 1, and the evaluation results are shown in Table 3.

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PCT/JP2011/053943 2010-03-18 2011-02-23 感光性導電ペーストおよび導電パターンの製造方法 WO2011114846A1 (ja)

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JP2011180580A (ja) * 2010-02-02 2011-09-15 Toray Ind Inc 有機−無機複合導電性パターン形成用感光性ペーストおよび有機−無機複合導電性パターンの製造方法
JP2013182800A (ja) * 2012-03-02 2013-09-12 Toray Ind Inc 感光性導電ペースト
JP2013195733A (ja) * 2012-03-21 2013-09-30 Toray Ind Inc 感光性導電ペースト
JP2013249467A (ja) * 2012-05-31 2013-12-12 Lg Chem Ltd 新規な高分子およびこれを含む着色組成物
JP2014228793A (ja) * 2013-05-24 2014-12-08 株式会社村田製作所 感光性ペースト
JP2015184626A (ja) * 2014-03-26 2015-10-22 東レ株式会社 感光性樹脂組成物、それからなる感光性樹脂ペーストならびにそれらを硬化させて得られる硬化膜およびそれを有する電極回路
US9963598B2 (en) 2011-02-23 2018-05-08 Dexerials Corporation Transparent conductive film, information input device, and electronic device
KR101865692B1 (ko) * 2015-10-08 2018-06-08 엘에스니꼬동제련 주식회사 감광성 도전 페이스트 조성물

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WO2013133272A1 (ja) * 2012-03-06 2013-09-12 デクセリアルズ株式会社 透明導電膜、導電性素子、組成物、入力装置、表示装置および電子機器
KR101473094B1 (ko) * 2012-05-31 2014-12-16 주식회사 엘지화학 신규한 고분자 및 이를 포함하는 착색 조성물
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CN108701509B (zh) * 2016-03-17 2020-02-07 东丽株式会社 层合部件及触摸面板
JP7044058B2 (ja) * 2016-03-31 2022-03-30 日本ゼオン株式会社 レジストパターン形成方法及びレジスト
CN109581814A (zh) * 2017-09-29 2019-04-05 互耐普勒斯有限公司 低温固化型感光树脂组合物

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Cited By (10)

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JP2011180580A (ja) * 2010-02-02 2011-09-15 Toray Ind Inc 有機−無機複合導電性パターン形成用感光性ペーストおよび有機−無機複合導電性パターンの製造方法
US9963598B2 (en) 2011-02-23 2018-05-08 Dexerials Corporation Transparent conductive film, information input device, and electronic device
US10100208B2 (en) 2011-02-23 2018-10-16 Dexerials Corporation Method of manufacturing a transparent conductive film
US10196526B2 (en) 2011-02-23 2019-02-05 Dexerials Corporation Transparent conductive film, information input device, and electronic device
JP2013182800A (ja) * 2012-03-02 2013-09-12 Toray Ind Inc 感光性導電ペースト
JP2013195733A (ja) * 2012-03-21 2013-09-30 Toray Ind Inc 感光性導電ペースト
JP2013249467A (ja) * 2012-05-31 2013-12-12 Lg Chem Ltd 新規な高分子およびこれを含む着色組成物
JP2014228793A (ja) * 2013-05-24 2014-12-08 株式会社村田製作所 感光性ペースト
JP2015184626A (ja) * 2014-03-26 2015-10-22 東レ株式会社 感光性樹脂組成物、それからなる感光性樹脂ペーストならびにそれらを硬化させて得られる硬化膜およびそれを有する電極回路
KR101865692B1 (ko) * 2015-10-08 2018-06-08 엘에스니꼬동제련 주식회사 감광성 도전 페이스트 조성물

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