WO2011114846A1 - Photosensitive conductive paste and method for forming conductive pattern - Google Patents

Photosensitive conductive paste and method for forming conductive pattern 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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WIPO (PCT)
Prior art keywords
photosensitive
conductive paste
glass transition
transition temperature
photosensitive conductive
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PCT/JP2011/053943
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French (fr)
Japanese (ja)
Inventor
水口創
草野一孝
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東レ株式会社
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Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2011509744A priority Critical patent/JPWO2011114846A1/en
Priority to KR1020127018020A priority patent/KR20130016192A/en
Priority to CN201180014597XA priority patent/CN102812399A/en
Publication of WO2011114846A1 publication Critical patent/WO2011114846A1/en

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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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Abstract

Disclosed are: a photosensitive conductive paste which is capable of providing a conductive pattern having a high conductivity and excellent flexibility at relatively low temperatures; and a method for forming a conductive pattern using the photosensitive conductive paste. Specifically disclosed is a photosensitive conductive paste which is characterized by containing (A) a compound that has an alkoxy group, (B) a photosensitive component that has an unsaturated double bond and a glass transition temperature within the range of 5-40˚C, (C) a photopolymerization initiator and (D) a conductive filler.

Description

感光性導電ペーストおよび導電パターンの製造方法Photosensitive conductive paste and method for producing conductive pattern
　本発明は屈曲性を有する導電パターンを形成するための感光性導電ペーストに関する。 The present invention relates to a photosensitive conductive paste for forming a conductive pattern having flexibility.
　本発明における導電パターンとは、樹脂を含む有機成分と導電性フィラー等を含む無機成分の両方を含有する導電パターンを指す。一般に、樹脂と導電性フィラーを含むペーストを塗布、乾燥した後に焼成することによって無機導電パターンを得ることができるが、５００℃以上の高温で焼成する必要があるため耐熱性の低い基板上に設けることができないといったような欠点を有する。一方、有機－無機複合導電パターンは比較的低温の処理で形成できるが、高い導電性を達成するのが比較的困難であった。 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. In general, an inorganic conductive pattern can be obtained by applying and drying a paste containing a resin and a conductive filler, followed by baking. However, since it is necessary to bake at 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. On the other hand, 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.
　従来、上述のような有機－無機複合導電パターンを形成するために、樹脂や接着剤の中に微粒子状の銀フレークや銅粉、あるいはカーボン粒子を多量に混合した、いわゆる導電ペーストが実用化されている。これらのものの多くはスクリーン印刷法によりパターンを形成し、加熱硬化により導電パターンとするものである（例えば、特許文献１、２参照）。しかしながら、スクリーン印刷法ではパターンの高精細化が困難であった。この問題を解決するために、酸性エッチング可能な導電ペースト（例えば、特許文献３参照）や紫外線硬化型の導電ペーストが開発されている。例えば感光性ポリイミド中に導電性微粒子を分散させたペーストを塗布、乾燥、露光、現像し、微細パターンを形成した後、キュアすることにより樹脂分を収縮させることで導電性微粒子を互いに接触させ、導電性を発現させるバンプ形成方法や（例えば、特許文献４参照）、同様に感光性フェノキシ樹脂中に銀粉を分散させた感光性導電ペーストを用いて導電性パッド、配線等を作製する方法などがある（例えば、特許文献５、６参照）。 Conventionally, in order to form the organic-inorganic composite conductive pattern as described above, a so-called conductive paste in which a large amount of fine particles of silver flakes, copper powder, or carbon particles are mixed in a resin or adhesive has been put into practical use. ing. Many of these are formed by a screen printing method and formed into a conductive pattern by heat curing (see, for example, Patent Documents 1 and 2). However, it has been difficult to achieve high definition patterns by screen printing. In order to solve this problem, a conductive paste capable of acid etching (see, for example, Patent Document 3) and an ultraviolet curable conductive paste have been developed. For example, 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).
　しかしながら、特許文献３記載の導電ペーストではフォトリソグラフィー法でパターン化を行うためには塗布膜上にレジスト層を形成する必要があり、工程数が多くなるという課題があった。特許文献４では導電性を発現させるために４００℃程度まで加熱する必要があり、使用する基材が限られるといった課題があった。また、特許文献５、６では感光性フェノキシ樹脂や感光性アクリル変性エポキシ樹脂を用い、低温で導電性を発現させることができるものの、得られる導電パターンの比抵抗値が高く、また５０μｍ以下の微細パターニングは困難であるといった課題があった。特許文献７、８では微細パターンが形成可能なものの特許文献７では導電性が低く、特許文献８記載の方法では導電性発現のためにアクリル（メタクリル）当量を小さくする必要があり、この方法で得られる導電パターンは脆いといった課題があった。 However, the conductive paste described in 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. In 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. In 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 μm or less. There was a problem that patterning was difficult. In 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.
　さらに、引用文献１～８記載の導電ペーストでは、得られる導電パターンの屈曲性が劣るため、フィルムなどのフレキシブルな基板上に導電パターンを設けた場合に剥がれや断線が発生し、導電性が低下してしまうという問題があった。 Furthermore, 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.
特願昭６３－７９７２７号公報Japanese Patent Application No. 63-79727 特願２００４－７３７４０号公報Japanese Patent Application No. 2004-73740 特願平８－２３７３８４号公報Japanese Patent Application No. 8-237384 特願平４－３２７４２３号公報Japanese Patent Application No. 4-327423 特願昭５８－１７５１０号公報Japanese Patent Application No. 58-17510 特願平３－２３８０２０号公報Japanese Patent Application No. 3-238020 特願２００１－３６２６３８号公報Japanese Patent Application No. 2001-362638 特願２００４－５６４４２２号公報Japanese Patent Application No. 2004-564422
　本発明の目的は上述の問題を解決し、比較的低温で高い導電性を有し、屈曲性に優れた導電パターンを得ることができる感光性導電ペーストおよびそれを用いて作製される導電パターンの製造方法を得ることである。 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.
　上述の課題を解決するため、本発明の感光性導電ペーストは以下の構成を有する。すなわち、アルコキシ基を有する化合物（Ａ）、不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）、光重合開始剤（Ｃ）、および導電性フィラー（Ｄ）を含むことを特徴とする感光性導電ペーストである。 In order to solve the above-described problems, 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.
　本発明によれば、比較的低温で高い導電性を有し、屈曲性に優れた導電パターンを容易に形成することができる。 According to the present invention, a conductive pattern having high conductivity at a relatively low temperature and excellent flexibility can be easily formed.
実施例の比抵抗率評価に用いたフォトマスクの透光パターンを示した模式図である。It is the schematic diagram which showed the translucent pattern of the photomask used for the specific resistivity evaluation of an Example. 実施例の屈曲性試験に用いたサンプルを模式的に示したものである。The sample used for the flexibility test of an Example is shown typically.
　本発明の感光性導電ペーストはアルコキシ基を有する化合物（Ａ）、不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）、光重合開始剤（Ｃ）を混合してなる感光性樹脂中に導電性フィラー（Ｄ）を分散させたものである。該ペーストは基板上に塗布し、乾燥させて溶媒を除去した後、露光、現像、キュア工程を経ることで基板上に所望の導電パターンを得ることができる感光性導電ペーストである。得られた導電パターンは有機－無機の複合物となっており、導電性フィラー同士がキュア時の硬化収縮により互いに接触することで導電性が発現する。 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.
　本発明の感光性導電ペーストに含まれるアルコキシ基を有する化合物（Ａ）とは、加熱によりアルコールを生じて縮合するアルコキシ基を分子内に有する化合物である。アルコキシ基としてはメトキシ基、エトキシ基、ブトキシ基、イソブトキシ基などが挙げられ、縮合時に生じるアルコールの分子量が比較的大きい方が好ましく、ブトキシ基、イソブトキシ基などが好ましく、少なくとも１以上のブトキシ基を有することがより好ましい。このような化合物（Ａ）の具体例としてはＮ－メトキシメチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、ブトキシエチルアクリレート、ブトキシトリエチレングリコールアクリレート、本州化学工業社製のＨＭＯＭ－ＴＰＨＡＰ、三和ケミカル社製のアルキル化アミノ化合物、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、ニカラックＭＷ－３０ＨＭ、ニカラックＭＷ－３９０、ニカラックＭＸ－２７０、ニカラックＭＸ－２８０、ニカラックＭＷ－１００ＬＭ、ニカラックＭＸ－７５０ＬＭなどが挙げられる。なお、ニカラックは登録商標である。 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. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, an isobutoxy group, and the like. Preferably, 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. Specific examples of 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.
　本発明の感光性導電ペーストに含まれるアルコキシ基を有する化合物（Ａ）の添加量としては、不飽和二重結合を有し、ガラス転移温度（以下Ｔｇとする。）が５～４０℃である感光性成分（Ｂ）１００重量部に対し、好ましくは１０～３００重量部の範囲で添加され、より好ましくは、５０～２００重量部である。不飽和二重結合を有し、Ｔｇが５～４０℃の範囲内である感光性成分（Ｂ）１００重量部に対する添加量が５０重量部以上とすることで特にキュア時の収縮量を大きくすることができ、導電性フィラー同士の接触確率を大きくすることができる。その結果、最終組成物である導電パターンの比抵抗率を低くすることができる。また、不飽和二重結合を有し、Ｔｇが５～４０℃の範囲内である感光性成分（Ｂ）１００重量部に対する添加量を２００重量部以下とすることにより、特に溶剤除去後のペースト組成物膜のタック性を小さくすることができ、導電パターンの欠点発生を抑制できるなどパターニングに優位に働く。 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. And 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. In addition, by adding 200 parts by weight or less 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 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.
　本発明で使用する不飽和二重結合を有し、Ｔｇが５～４０℃の範囲内である感光性成分（Ｂ）は分子内に不飽和二重結合を少なくとも一つ以上有するモノマー、オリゴマーもしくはポリマーのことをいい、１種または２種以上使用することができる。感光性成分（Ｂ）は特に限定されないが、本発明のパターン加工の現像には有機溶媒ではなくアルカリ水溶液による現像が好ましいため、アルカリ可溶性のポリマーを含むことが望ましい。 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. Although 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.
　アルカリ可溶性のポリマーとしては、アクリル系共重合体があげられる。アクリル系共重合体とは、共重合成分に少なくともアクリル系モノマーを含む共重合体であり、アクリル系モノマーの具体例としては炭素－炭素二重結合を有するすべての化合物が使用可能であるが、好ましくはメチルアクリレート、アクリル酸、アクリル酸２－エチルヘキシル、メタクリル酸エチル、ｎ－ブチルアクリレート、i－ブチルアクリレート、i－プロパンアクリレート、グリシジルアクリレート、Ｎ－メトキシメチルアクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、ブトキシトリエチレングリコールアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、２－ヒドロキシエチルアクリレート、イソボニルアクリレート、２－ヒドロキシプロピルアクリレート、イソデキシルアクリレート、イソオクチルアクリレート、ラウリルアクリレート、２－メトキシエチルアクリレート、メトキシエチレングリコールアクリレート、メトキシジエチレングリコールアクリレート、オクタフロロペンチルアクリレート、フェノキシエチルアクリレート、ステアリルアクリレート、トリフロロエチルアクリレート、アクリルアミド、アミノエチルアクリレート、フェニルアクリレート、フェノキシエチルアクリレート、１－ナフチルアクリレート、２－ナフチルアクリレート、チオフェノールアクリレート、ベンジルメルカプタンアクリレートなどのアクリル系モノマーおよびこれらのアクリレートをメタクリレートに代えたものやスチレン、ｐ－メチルスチレン、ｏ－メチルスチレン、ｍ－メチルスチレン、α－メチルスチレン、クロロメチルスチレン、ヒドロキシメチルスチレンなどのスチレン類、γ－メタクリロキシプロピルトリメトキシシラン、１－ビニル－２－ピロリドンなどが挙げられる。 Examples of the alkali-soluble polymer 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. Preferably 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, phenoxyethyl acrylate, stearyl acrylate, trifluoroethyl Acrylic monomers such as acrylate, acrylamide, aminoethyl acrylate, phenyl acrylate, phenoxyethyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, thiophenol acrylate, benzyl mercaptan acrylate, and those obtained by replacing these acrylates with methacrylate, styrene, p-methylstyrene Styrenes such as o-methylstyrene, m-methylstyrene, α-methylstyrene, chloromethylstyrene, hydroxymethylstyrene, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like.
　本発明で使用される不飽和二重結合を有し、Ｔｇが５～４０℃の範囲内である感光性成分（Ｂ）のガラス転移温度は、感光性成分の示差走査熱量計（ＤＳＣ）測定によって求めることもできるが、共重合成分であるモノマーの共重合比率およびそれぞれのモノマーのホモポリマーのガラス転移温度を用いて下記の式（１）により算出でき、本発明ではこの値を用いた。 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. However, it can be calculated by the following formula (1) using the copolymerization ratio of the monomer as a copolymerization component and the glass transition temperature of the homopolymer of each monomer, and this value was used in the present invention.
Figure JPOXMLDOC01-appb-M000001
Figure JPOXMLDOC01-appb-M000001
ここで、Ｔｇはポリマーのガラス転移温度（単位：Ｋ）、Ｔ１、Ｔ２、Ｔ３・・・はモノマー１、モノマー２、モノマー３・・・のホモポリマーのガラス転移温度（単位：Ｋ）、Ｗ１、Ｗ２、Ｗ３・・・はモノマー１、モノマー２、モノマー３・・・の重量基準の共重合比率である。 Here, 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,.
　本発明で使用する不飽和二重結合を有し、Ｔｇが５～４０℃の範囲内である感光性成分（Ｂ）のガラス転移温度は５～４０℃であることが必要であり、１０～３０であることが好ましい。Ｔｇが５℃以上であると乾燥膜のタック性を抑制することができ、さらに１０℃以上であると特に温度変化に対する形状安定性が高くなる。また、Ｔｇが４０℃以下であると室温において屈曲性を発現し、さらに３０℃以下であると屈曲時の内部応力を緩和することができ、特にクラックの発生を抑制することができる。 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. When 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.
　本発明で使用される不飽和二重結合を有し、Ｔｇが５～４０℃の範囲内である感光性成分（Ｂ）の酸価はアルカリ水溶液での現像という観点から５０～２００ｍｇＫＯＨ／ｇであることが好ましく、８０～１５０ｍｇＫＯＨ／ｇであることがより好ましい。酸価が８０ｍｇＫＯＨ／ｇ以上であると可溶部分の現像液に対する溶解性が低下することがなく、酸価が１５０ｍｇＫＯＨ／ｇ以下であると現像許容幅を広くすることができる。なお、酸価の測定は、ＪＩＳ－Ｋ００７０（１９９２）に準拠して求める。 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).
　本発明の感光性導電ペーストに含まれる光重合開始剤（Ｃ）とは紫外線などの短波長の光を吸収し、分解してラジカルを生じる化合物のことをいう。具体例としては、１，２－オクタンジオン、１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、エタノン、１－［９－エチル－６－２（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、ベンゾフェノン、ｏ－ベンゾイル安息香酸メチル、４，４′－ビス（ジメチルアミノ）ベンゾフェノン、４，４′－ビス（ジエチルアミノ）ベンゾフェノン、４，４′－ジクロロベンゾフェノン、４－ベンゾイル－４′－メチルジフェニルケトン、ジベンジルケトン、フルオレノン、２，２′－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、２－ヒドロキシ－２－メチルプロピオフェノン、ｐ－ｔ－ブチルジクロロアセトフェノン、チオキサントン、２－メチルチオキサントン、２－クロロチオキサントン、２－イソプロピルチオキサントン、ジエチルチオキサントン、ベンジル、ベンジルジメチルケタール、ベンジル－β－メトキシエチルアセタール、ベンゾイン、ベンゾインメチルエーテル、ベンゾインブチルエーテル、アントラキノン、２－ｔ－ブチルアントラキノン、２－アミルアントラキノン、β－クロルアントラキノン、アントロン、ベンズアントロン、ジベンゾスベロン、メチレンアントロン、４－アジドベンザルアセトフェノン、２，６－ビス（ｐ－アジドベンジリデン）シクロヘキサノン、６－ビス（ｐ－アジドベンジリデン）－４－メチルシクロヘキサノン、１－フェニル－１，２－ブタンジオン－２－（ｏ－メトキシカルボニル）オキシム、１－フェニル－プロパンジオン－２－（ｏ－エトキシカルボニル）オキシム、１－フェニル－プロパンジオン－２－（ｏ－ベンゾイル）オキシム、１，３－ジフェニル－プロパントリオン－２－（ｏ－エトキシカルボニル）オキシム、１－フェニル－３－エトキシ－プロパントリオン－２－（ｏ－ベンゾイル）オキシム、ミヒラーケトン、２－メチル－［４－（メチルチオ）フェニル］－２－モルフォリノ－１－プロパノン、ナフタレンスルホニルクロライド、キノリンスルホニルクロライド、Ｎ－フェニルチオアクリドン、４，４′－アゾビスイソブチロニトリル、ジフェニルジスルフィド、ベンズチアゾールジスルフィド、トリフェニルホスフィン、カンファーキノン、四臭化炭素、トリブロモフェニルスルホン、過酸化ベンゾインおよびエオシン、メチレンブルーなどの光還元性色素とアスコルビン酸、トリエタノールアミンなどの還元剤の組み合わせなどが挙げられるが、特にこれらに限定されない。本発明ではこれらを１種または２種以上使用することができる。また、中でもアルコキシ基を有する化合物（Ａ）のアルコキシ基による縮合反応を促進するという観点から分子内にベンゾイル骨格を有しているものが好ましく、１，２－オクタンジオン、１－［４－（フェニルチオ）－２－（Ｏ－ベンゾイルオキシム）］、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、エタノン、または、１－［９－エチル－６－２（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）が特に好ましい。 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. 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 (diethylamino) benzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenyl ketone , Dibenzyl ketone, fluorenone, 2,2'-diethoxyacetophenone, 2,2- Methoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl Ketal, benzyl-β-methoxyethyl acetal, benzoin, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzosuberone, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 6-bis (p-azidobenzyl) Den) -4-methylcyclohexanone, 1-phenyl-1,2-butanedione-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-propane Dione-2- (o-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-benzoyl) oxime, Michler's ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-phenylthioacridone, 4,4′-azobisisobutyronitrile, Diphenyl disulfide, benzthiazole di Examples include combinations of photoreductive dyes such as rufide, triphenylphosphine, camphorquinone, carbon tetrabromide, tribromophenylsulfone, benzoin peroxide and eosin, methylene blue, and reducing agents such as ascorbic acid and triethanolamine. However, it is not particularly limited to these. In the present invention, one or more of these can be used. Among them, those having a benzoyl skeleton in the molecule are preferred from the viewpoint of promoting the condensation reaction by the alkoxy group of the compound (A) having an alkoxy group, and 1,2-octanedione, 1- [4- ( Phenylthio) -2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphine oxide, ethanone, or 1- [9-ethyl-6-2 (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) Is particularly preferred.
　光重合開始剤（Ｃ）の添加量としては、不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対し、好ましくは０．０５～３０重量部の範囲で添加され、より好ましくは、５～２０重量部である。不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対する光重合開始剤（Ｃ）の添加量を５重量部以上とすることにより、特に露光部の硬化密度が増加し、現像後の残膜率を高くすることができる。また、不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対する光重合開始剤（Ｃ）の添加量を２０重量部以下とすることで、特に光重合開始剤（Ｃ）による塗布膜上部での過剰な光吸収を抑制し、導電パターンが逆テーパー形状となり基材との接着性が低下することを抑制することができる。 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. By making 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. Further, 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. In particular, it is possible to suppress excessive light absorption at the upper part of the coating film by the photopolymerization initiator (C), and to prevent the conductive pattern from having a reverse taper shape and lowering the adhesion to the substrate.
　本発明のペーストは光重合開始剤（Ｃ）と共に増感剤を添加して感度を向上させたり、反応に有効な波長範囲を拡大したりすることができる。 In the paste of the present invention, 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.
　増感剤の具体例としては、２，４－ジエチルチオキサントン、イソプロピルチオキサントン、２，３－ビス（４－ジエチルアミノベンザル）シクロペンタノン、２，６－ビス（４－ジメチルアミノベンザル）シクロヘキサノン、２，６－ビス（４－ジメチルアミノベンザル）－４－メチルシクロヘキサノン、ミヒラーケトン、４，４－ビス（ジエチルアミノ）ベンゾフェノン、４，４－ビス（ジメチルアミノ）カルコン、４，４－ビス（ジエチルアミノ）カルコン、ｐ－ジメチルアミノシンナミリデンインダノン、ｐ－ジメチルアミノベンジリデンインダノン、２－（ｐ－ジメチルアミノフェニルビニレン）イソナフトチアゾール、１，３－ビス（４－ジメチルアミノフェニルビニレン）イソナフトチアゾール、１，３－ビス（４－ジメチルアミノベンザル）アセトン、１，３－カルボニルビス（４－ジエチルアミノベンザル）アセトン、３，３－カルボニルビス（７－ジエチルアミノクマリン）、Ｎ－フェニル－Ｎ－エチルエタノールアミン、Ｎ－フェニルエタノールアミン、Ｎ－トリルジエタノールアミン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、３－フェニル－５－ベンゾイルチオテトラゾール、１－フェニル－５－エトキシカルボニルチオテトラゾールなどが挙げられる。本発明ではこれらを１種または２種以上使用することができる。増感剤を本発明の感光性導電ペーストに添加する場合、その添加量は不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対して通常０．０５～１０重量部の範囲内であることが好ましく、より好ましくは０．１～１０重量部である。不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対する添加量を０．１重量部以上とすることにより光感度を向上させる効果が十分に発揮されやすく、不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対する添加量を１０重量部以下とすることにより、特に塗布膜上部での過剰な光吸収が起こり、導電パターンが逆テーパー形状となり、基材との接着性が低下することを抑制することができる。 Specific examples of the sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2,6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) Chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole 1,3-bis (4-dimethyl) Aminobenzal) acetone, 1,3-carbonylbis (4-diethylaminobenzal) acetone, 3,3-carbonylbis (7-diethylaminocoumarin), N-phenyl-N-ethylethanolamine, N-phenylethanolamine, N- Examples include tolyldiethanolamine, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 3-phenyl-5-benzoylthiotetrazole, and 1-phenyl-5-ethoxycarbonylthiotetrazole. In the present invention, one or more of these can be used. When a sensitizer is added to the photosensitive conductive paste of the present invention, 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. Usually, 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. 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.
　本発明の感光性導電ペーストに含まれる導電性フィラー（Ｄ）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、これらの導電性フィラーを単独、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。 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. Moreover, the electroconductive particle which coat | covered the surface of the insulating particle or electroconductive particle with the above-mentioned component can be used similarly. Among these, Ag, Cu and Au are preferable from the viewpoint of conductivity, and Ag is more preferable from the viewpoint of cost and stability.
　導電性フィラー（Ｄ）の平均粒子径は０．５～１０μｍが好ましく、より好ましくは１～６μｍである。平均粒子径が１μｍ以上であると導電性フィラー同士の接触確率が向上し、作製される導電パターンの比抵抗値、および断線確率を低くすることができ、且つ露光時の紫外線が膜中をスムーズに透過することができ、微細パターニングが容易となる。また平均粒子径が６μｍ以下であれば印刷後の回路パターンの表面平滑度、パターン精度、寸法精度が向上する。なお、平均粒子径は、コールターカウンター法、光子相関法およびレーザー回折法等により体積平均粒子径を求めることができる。 The average particle diameter of the conductive filler (D) is preferably 0.5 to 10 μm, more preferably 1 to 6 μm. When the average particle size is 1 μm 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. If the average particle size is 6 μm 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.
　導電性フィラー（Ｄ）の添加量としては感光性導電ペースト中の全固形分に対し、７０～９５重量％の範囲内であることが好ましく、より好ましくは８０～９０重量％である。８０重量％以上とすることにより、特にキュア時の硬化収縮における導電性フィラー同士の接触確率が向上し、作製される導電パターンの比抵抗値、および断線確率を低くすることができる。また、９０重量％以下とすることにより、特に露光時の紫外線が膜中をスムーズに透過することができ、微細なパターニングが容易となる。また、固形分とは感光性導電ペーストから溶剤を除いたものである。 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. By setting it as 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. In addition, 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.
　本発明の感光性導電ペーストに含まれる酸発生剤（Ｅ）は、光もしくは熱により反応し、酸を発生する物質のことをいう。発生する酸による触媒効果により、アルコキシ基を有する化合物（Ａ）中のアルコキシ基の縮合反応を低温で促進させる効果を有する。その結果、より低温のキュア条件において導電性を発現させ、且つ比抵抗率を小さくすることができる。 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.
　光酸発生剤としてはキノンジアジド系、ジアゾジスルホン系、トリフェニルスルホニウム系の物質が挙げられ、熱酸発生剤としてはスルホニウム塩などが挙げられる。光酸発生剤は露光により露光部に酸を発生させるため、露光部と未露光部との溶解度差が小さくなり、パターニング性に悪影響を与える可能性があるため熱酸発生剤が好ましく、発生する酸の強さの観点からスルホニウム塩がより好ましい。 Examples of photoacid generators include quinonediazide, diazodisulfone, and triphenylsulfonium substances, and examples of thermal acid generators 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.
　酸発生剤（Ｅ）の添加量としては不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対して０．０１～５重量部の範囲内であることが好ましく、より好ましくは０．０５～５重量部である。不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対する添加量を０．０５重量部以上とすることにより、特にアルコキシ基を有する化合物のアルコキシ基の縮合反応の触媒としての働きが顕著になる。また、５重量部以下とすることにより触媒としての効率が高くなる。 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. By adding 0.05 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., a compound having an alkoxy group in particular. The function as a catalyst for the condensation reaction of the alkoxy group becomes remarkable. Moreover, the efficiency as a catalyst becomes high by setting it as 5 weight part or less.
　本発明の感光性導電ペーストに含まれる全塩素含有量が３００ｐｐｍ以上である化合物（Ｆ）は化合物中に含まれる全塩素量が３００ｒｐｍ以上であれば特に限定されない。本発明において全塩素量とは、化合物中に含まれる塩素イオン、塩素原子のすべての含有量を指し、単独で存在しているか、構造中に取り込まれているか、またどのような態様で存在しているかは問わない。また、これら塩素イオン、塩素原子の由来元は特段限定されない。 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. In the present invention, 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.
　全塩素含有量が３００ｐｐｍ以上である化合物（Ｆ）としてはエピクロルヒドリン由来の化合物であるグリシジル基含有化合物、その不飽和二重結合付加物などが挙げられる。具体例として、グリシジル基含有化合物としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、水添ビスフェノール型エポキシ樹脂、ビスフェノールフルオレン型エポキシ樹脂、ビスクレゾールフルオレン型エポキシ樹脂、ビスフェノキシエタノールフルオレン型エポキシ樹脂、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レソルシノールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、水添ビスフェノールＡ型ジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、アリルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、フェニルグリシジルエーテル、ポリブタジエンジグリシジルエーテル、ジグリシジルｏ－フタレート、ヒドロキノンジグリシジルエーテル、ジグリシジルテレフタレート、Ｎ－グリシジルフタルイミド、トリメチロールプロパントリグリシジルエーテルが挙げられ、不飽和二重結合付加物としてはこれらグリシジル基含有化合物のアクリル酸付加物、メタクリル酸付加物などが挙げられる。 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, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, polybutadiene diglycidyl ether, diglycidyl o-phthalate, hydroquinone diglycidyl ether, diglycidyl terephthalate, N-glycidyl phthalimide, trimethylolpropane triglycidyl ether, As unsaturated double bond adducts, these glycidyl Acrylic acid adduct containing compound, and a methacrylic acid adduct.
　全塩素含有量が３００ｐｐｍ以上である化合物（Ｆ）の添加量としては不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対し、好ましくは０．０５～３０重量部の範囲で添加され、より好ましくは、０．５～２０重量部である。不飽和二重結合を有し、ガラス転移温度が５～４０℃である感光性成分（Ｂ）１００重量部に対する化合物（Ｆ）の添加量を０．０５重量部以上とすることにより、最終組成物の導電性を高めることができ、化合物（Ｆ）の添加量を３０重量部以下とすることにより現像マージン、高温高湿度下での密着性をよくすることができる。 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. By adding 0.05 part by weight or more of compound (F) to 100 parts by weight of photosensitive component (B) having an unsaturated double bond and a glass transition temperature of 5 to 40 ° C., 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.
　本発明の感光性導電ペーストの導電性フィラー（Ｄ）を除く全固形分量における全塩素含有量は１００ｐｐｍ以上であることが、最終組成物の導電性を高くすることが出きるため好ましい。 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.
　化合物（Ｆ）、本発明の感光性導電ペーストの導電性フィラー（Ｄ）を除く全固形分量における全塩素含有量は塩素分析装置を用いて測定することができる。化合物（Ｆ）については溶剤で１００倍に希釈したものを測定試料とし、本発明の感光性導電ペーストについては遠心分離を行い、得られた上澄み溶液を乾燥し、得られた有機成分を再度溶剤で１００倍に希釈したものを測定試料とした。なお導電性フィラー（Ｄ）を除く全固形分量については感光性導電ペーストの乾燥膜の熱重量分析（ＴＧ測定）を行い、重量減少率を用いて算出した。 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. In addition, about the total solid content except a conductive filler (D), the thermogravimetric analysis (TG measurement) of the dry film | membrane of the photosensitive electrically conductive paste was performed, and it computed using the weight decreasing rate.
　本発明の感光性導電ペーストは溶剤を含有してもよい。溶剤としては、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ－メチル－２－ピロリドン、ジメチルイミダゾリジノン、ジメチルスルホキシド、γ－ブチロラクトン、乳酸エチル、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、エチレングリコールモノ－ｎ－プロピルエーテル、ジアセトンアルコール、テトラヒドロフルフリルアルコール、プロピレングリコールモノメチルエーテルアセテートなどが挙げられる。溶剤は１種を単独で用いたり、２種以上を混合して用いたりすることができる。溶剤はペースト作製後、粘度調整を目的に後から添加してもかまわない。 The photosensitive conductive paste of the present invention may contain a solvent. Examples of the solvent include N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethylimidazolidinone, dimethyl sulfoxide, γ-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.
　本発明の感光性導電ペーストは、その所望の特性を損なわない範囲であれば分子内に不飽和二重結合を有しない非感光性ポリマー、可塑剤、レベリング剤、界面活性剤、シランカップリング剤、消泡剤、顔料等の添加剤を配合することもできる。非感光性ポリマーの具体例としてはエポキシ樹脂、ノボラック樹脂、フェノール樹脂、ポリイミド前駆体、既閉環ポリイミドなどが挙げられる。 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. Specific examples of the non-photosensitive polymer include epoxy resin, novolac resin, phenol resin, polyimide precursor, and closed ring polyimide.
　可塑剤の具体例としてはジブチルフタレート、ジオクチルフタレート、ポリエチレングリコール、グリセリン等が挙げられる。レベリング剤の具体例としては特殊ビニル系重合物、特殊アクリル系重合物などが挙げられる。 Specific examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, glycerin and the like. Specific examples of the leveling agent include a special vinyl polymer and a special acrylic polymer.
　シランカップリング剤としては、メチルトリメトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ヘキサメチルジシラザン、３－メタクリロキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、ビニルトリメトキシシランなどが挙げられる。 As silane coupling agents, methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane Etc.
　本発明の感光性導電ペーストは分散機、混練機などを用いて作製される。これらの具体例としては三本ローラー、ボールミル、遊星式ボールミルなどが挙げられるが、これらに限定されない。
次に本発明の感光性導電ペーストを用いた導電パターンの製造方法について説明する。導電パターンを作製するためには本発明のペーストを基板上に塗布し、加熱して溶剤を揮発させて乾燥する。その後パターン形成用マスクを介し、露光し、現像工程を経ることで基板上に所望のパターンを形成する。そしてキュアして導電パターンを作製する。 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.
Next, the manufacturing method of the conductive pattern using the photosensitive electrically conductive paste of this invention is demonstrated. In order to produce a conductive pattern, 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.
　本発明で用いる基板は、例えば、シリコンウエハー、セラミックス基板、有機系基板などが挙げられる。セラミックス基板としては、ガラス基板、アルミナ基板、窒化アルミニウム基板、炭化ケイ素基板等が挙げられ、樹脂基板としては、エポキシ樹脂基板、ポリエーテルイミド樹脂基板、ポリエーテルケトン樹脂基板、ポリサルフォン系樹脂基板、ポリイミドフィルム、ポリエステルフィルム、アラミドフィルム等が挙げられるが、これらに限定されない。 Examples of the substrate used in the present invention include a silicon wafer, a ceramic substrate, and an organic substrate. Examples of the ceramic substrate include a glass substrate, an alumina substrate, an aluminum nitride substrate, and a silicon carbide substrate. Examples of the resin substrate include an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, 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.
　本発明の感光性導電ペーストを基板に塗布する方法としてはスピナーを用いた回転塗布、スプレー塗布、ロールコーティング、スクリーン印刷、ブレードコーター、ダイコーター、カレンダーコーター、メニスカスコーター、バーコーターなどの方法がある。また、塗布膜厚は、塗布手法、組成物の固形分濃度、粘度などによって異なるが、通常、乾燥後の膜厚が、０．１～５０μｍの範囲内になるように塗布される。 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 μm.
　次に基板上に塗布した塗布膜から溶剤を除去する。溶剤を除去する方法としては、オーブン、ホットプレート、赤外線などによる加熱乾燥や真空乾燥などが挙げられる。加熱乾燥は５０℃から１８０℃の範囲で１分から数時間行うのが好ましい。 Next, the solvent is removed from the coating film applied on the substrate. Examples of 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.
　溶剤除去後の塗布膜上に、フォトリソグラフィー法によりパターン加工を行う。露光に用いられる光源としては水銀灯のｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）を用いるのが好ましい。 The pattern is processed by photolithography on the coating film after removing the solvent. As 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.
　露光後、現像液を用いて未露光部を除去することによって、所望のパターンが得られる。アルカリ現像を行う場合の現像液としては、水酸化テトラメチルアンモニウム、ジエタノールアミン、ジエチルアミノエタノール、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、トリエチルアミン、ジエチルアミン、メチルアミン、ジメチルアミン、酢酸ジメチルアミノエチル、ジメチルアミノエタノール、ジメチルアミノエチルメタクリレート、シクロヘキシルアミン、エチレンジアミン、ヘキサメチレンジアミンなどの化合物の水溶液が好ましい。また場合によっては、これらの水溶液にＮ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、γ－ブチロラクトンなどの極性溶媒、メタノール、エタノール、イソプロパノールなどのアルコール類、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートなどのエステル類、シクロペンタノン、シクロヘキサノン、イソブチルケトン、メチルイソブチルケトンなどのケトン類などを単独あるいは複数種添加したものを現像液として用いてもよい。また、これらのアルカリ水溶液に界面活性剤を添加したものを現像液として使用することもできる。有機現像を行う場合の現像液としては、Ｎ－メチル－２－ピロリドン、Ｎ－アセチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホルトリアミドなどの極性溶媒を単独あるいは、メタノール、エタノール、イソプロピルアルコール、キシレン、水、メチルカルビトール、エチルカルビトールなどと組み合わせた混合溶液が使用できる。 After exposure, a desired pattern can be obtained by removing unexposed portions using a developer. 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. In some cases, these aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and γ-butyrolactone, alcohols such as methanol, ethanol and isopropanol. , Esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be used alone or as a developer. Moreover, what added surfactant to these alkaline aqueous solution can also be used as a developing solution. 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.
　現像は、基板を静置または回転させながら上記の現像液を塗布膜面にスプレーする、基板を現像液中に浸漬する、あるいは浸漬しながら超音波をかけるなどの方法によって行うことができる。 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.
　現像後、水によるリンス処理を施してもよい。ここでもエタノール、イソプロピルアルコールなどのアルコール類、乳酸エチル、プロピレングリコールモノメチルエーテルアセテートなどのエステル類などを水に加えてリンス処理をしてもよい。 After the development, a rinsing treatment with water may be performed. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.
　次にアルコキシ基を有する化合物（Ａ）中のアルコキシ基の縮合反応を行うためにペースト組成物膜をキュアする。キュアする方法としては、オーブン、イナートオーブン、ホットプレート、赤外線などによる加熱乾燥や真空乾燥などが挙げられる。キュア温度は１３０～４００℃の範囲が好ましく、より好ましくは１５０～４００℃である。キュア温度を１５０℃以上とすることにより、特にアルコキシ基を有する化合物（Ａ）の縮合反応の反応率を向上させることができ、その結果、導電性フィラー同士の接触確率が上がり、比抵抗率が小さくなる。また、本発明の感光性導電ペーストは４００℃以下の比較的低温のキュアで高い導電性を得ることができるため、耐熱性が低い基板上や、耐熱性の低い材料と併用して用いることができる。このようにキュア工程を経て導電パターンを作製することができる。 Next, 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. Examples of 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. In addition, since 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.
　以下、本発明の実施例について説明するが、本発明はこれらによって限定されるものではない。各実施例および比較例で用いた材料および評価方法は以下の通りである。 Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. The materials and evaluation methods used in each example and comparative example are as follows.
　＜パターニング性の評価方法＞
　ガラス基板上に感光性導電ペーストを乾燥厚みが１２μmになるように塗布、１００℃のホットプレートで３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、そして１８０℃で１時間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。 <Patternability evaluation method>
A photosensitive conductive paste is applied on a glass substrate so that the dry thickness is 12 μm, 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). (Represents (μm) / interval (μm)). The pattern is observed with an optical microscope, a pattern having a minimum L / S value with no residue between patterns and no pattern peeling is confirmed, and this minimum L / S value can be developed as L / S. did.
　＜比抵抗率の評価方法＞
　１００℃のホットプレートで３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、現像そして１８０℃で１時間乾燥オーブン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、下記の計算式に当てはめて比抵抗率を算出した。なお膜厚の測定は触針式段差計“サーフコム１４００”（商品名、（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／ｓ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。
比抵抗率＝表面抵抗値×膜厚×線幅／ライン長
　＜屈曲性の評価方法＞
　図２は屈曲性試験に用いたサンプルを模式的に示したものである。縦１０ｍｍ、横１００ｍｍの長方形のポリイミドフィルム（厚み５０μｍ）上に感光性導電ペーストを乾燥厚みが１０μｍになるように塗布し、１００℃のホットプレートで３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、１８０℃で１時間乾燥オーブン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％以下であること、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○とし、そうでないものを×とした。 <Evaluation method of specific resistivity>
Drying on a hot plate at 100 ° C. for 3 minutes, exposure through a photomask having a light-transmitting part A having the pattern shown in FIG. 1, development and curing in a drying oven at 180 ° C. for 1 hour for specific resistivity measurement A conductive pattern was obtained. The line width of the conductive pattern is 0.400 mm, and the line length is 80 mm. The ends of the obtained pattern were connected with a surface resistance meter, the surface resistance value was measured, and the specific resistivity was calculated by applying to the following calculation formula. The film thickness was measured using a stylus step meter “Surfcom 1400” (trade name, 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 / s. 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.
Specific resistivity = surface resistance value × film thickness × line width / line length <Flexibility Evaluation Method>
FIG. 2 schematically shows a sample used for the flexibility test. A photosensitive conductive paste is applied onto a rectangular polyimide film (thickness 50 μm) having a length of 10 mm and a width of 100 mm so as to have a dry thickness of 10 μm, 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. After that, 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. As a result, 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.
　実施例、比較例で用いた材料は以下の通りである。
・アルコキシ基を有する化合物（Ａ）
Ｎ－ｎ－ブトキシメチルアクリルアミド
ＢＸ－４０００（商品名、株式会社三和ケミカル社製）
・感光性成分
以下のアクリルモノマーを用い、合成例１～５の方法で得られた感光性成分Ｂ－１～Ｂ－５を用いた。
メチルメタクリレート（ＭＭＡ）（ホモポリマーのガラス転移温度：１０５℃）
エチルアクリレート（ＥＡ）（ホモポリマーのガラス転移温度：－２２℃）
アクリル酸（ＡＡ）（ホモポリマーのガラス転移温度：１０６℃）
シクロメタクリレート（ＣＭＡ）（ホモポリマーのガラス転移温度：－６５℃）
スチレン（Ｓｔ）（ホモポリマーのガラス転移温度：１００℃）
メタクリル酸２－エチルヘキシル（２－ＥＨＭＡ）（ホモポリマーのガラス転移温度：－１０℃）
i－ブチルアクリレート（i－ＢＡ）（ホモポリマーのガラス転移温度：－２４℃）
グリシジルメタクリレート（ＧＭＡ）（ホモポリマーのガラス転移温度：７４℃） The materials used in Examples and Comparative Examples are as follows.
.Compound having an alkoxy group (A)
Nn-butoxymethylacrylamide BX-4000 (trade name, manufactured by Sanwa Chemical Co., Ltd.)
The photosensitive components B-1 to B-5 obtained by the methods of Synthesis Examples 1 to 5 were used using the acrylic monomers below the photosensitive components.
Methyl methacrylate (MMA) (glass transition temperature of homopolymer: 105 ° C.)
Ethyl acrylate (EA) (glass transition temperature of homopolymer: −22 ° C.)
Acrylic acid (AA) (Homopolymer glass transition temperature: 106 ° C.)
Cyclomethacrylate (CMA) (Glass transition temperature of homopolymer: -65 ° C)
Styrene (St) (Homopolymer glass transition temperature: 100 ° C.)
2-ethylhexyl methacrylate (2-EHMA) (glass transition temperature of homopolymer: −10 ° C.)
i-Butyl acrylate (i-BA) (Glass transition temperature of homopolymer: -24 ° C)
Glycidyl methacrylate (GMA) (glass transition temperature of homopolymer: 74 ° C.)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（合成例１）感光性成分Ｂ－１
　共重合比率（重量基準）：ＥＡ／２－ＥＨＭＡ／Ｓｔ／ＧＭＡ／ＡＡ＝２０／４０／２０／５／１５
　窒素雰囲気の反応容器中にγ－ＢＬ１５０ｇを仕込みオイルバスを用いて８０℃まで昇温した。これに、エチルアクリレート２０ｇ、メタクリル酸２－エチルヘキシル４０ｇ、スチレン２０ｇ、アクリル酸１５ｇ、２，２’－アゾビスイソブチロニトリル０．８ｇおよびγ－ＢＬ１０ｇからなる混合物を１時間かけて滴下した。滴下終了後、さらに６時間重合反応を行った。その後、ハイドロキノンモノメチルエーテル１ｇを添加して重合反応を停止した。引き続きグリシジルメタクリレート５ｇ、トリエチルベンジルアンモニウムクロライド１ｇおよびγ－ＢＬ１０ｇからなる混合物を０．５時間かけて滴下した。滴下終了後、さらに２時間付加反応を行った。得られた反応溶液をメタノールで精製することで未反応不純物を除去し、さらに２４時間真空乾燥することで感光性成分Ｂ－１を得た。得られた感光性成分Ｂ－１の酸価は１０３ｍｇＫＯＨ／ｇ、式（１）より求めたガラス転移温度は２１．７℃であった。 (Synthesis Example 1) Photosensitive Component B-1
Copolymerization ratio (weight basis): EA / 2-EHMA / St / GMA / AA = 20/40/20/5/15
In a nitrogen atmosphere reaction vessel, 150 g of γ-BL was charged and heated to 80 ° C. using an oil bath. To this was added dropwise a mixture of 20 g of ethyl acrylate, 40 g of 2-ethylhexyl methacrylate, 20 g of styrene, 15 g of acrylic acid, 0.8 g of 2,2′-azobisisobutyronitrile and 10 g of γ-BL over 1 hour. After completion of the dropping, a polymerization reaction was further performed for 6 hours. Thereafter, 1 g of hydroquinone monomethyl ether was added to terminate the polymerization reaction. Subsequently, a mixture consisting of 5 g of glycidyl methacrylate, 1 g of triethylbenzylammonium chloride and 10 g of γ-BL was added dropwise over 0.5 hours. After completion of the dropwise addition, an additional reaction was performed for 2 hours. The resulting reaction solution was purified with methanol to remove unreacted impurities, and further dried under vacuum for 24 hours to obtain photosensitive component B-1. The obtained photosensitive component B-1 had an acid value of 103 mgKOH / g and a glass transition temperature obtained from the formula (1) of 21.7 ° C.
　（合成例２）感光性成分Ｂ－２
　共重合比率（重量基準）：ＭＡ／ＣＭＡ／i－ＢＡ／ＧＭＡ／ＡＡ＝２５／２５／３０／５／１５
　合成例１と同様にメチルアクリレート２５ｇ、シクロメタクリレート２５ｇ、イソブチルアクリレート３０ｇ、アクリル酸１５ｇにグリシジルメタクリレートを５ｇ付加した感光性成分Ｂ－２を得た。得られた感光性成分Ｂ－２の酸価は９８ｍｇＫＯＨ／ｇ、式（１）より求めたガラス転移温度は３６．５℃であった。 (Synthesis Example 2) Photosensitive Component B-2
Copolymerization ratio (weight basis): MA / CMA / i-BA / GMA / AA = 25/25/30/5/15
As in Synthesis Example 1, 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.
　（合成例３）感光性成分Ｂ－３
　共重合比率（重量基準）：Ｓｔ／ＣＭＡ／i－ＢＡ／ＧＭＡ／ＡＡ＝２５／２５／２５／５／２０
　合成例１と同様にスチレン２５ｇ、シクロメタクリレート２５ｇ、イソブチルアクリレート２５ｇ、アクリル酸２０ｇにグリシジルメタクリレートを５ｇ付加した感光性成分Ｂ－３を得た。得られた感光性成分Ｂ－３の酸価は１５２ｍｇＫＯＨ／ｇ、式（１）より求めたガラス転移温度は３２．７℃であった。 (Synthesis Example 3) Photosensitive Component B-3
Copolymerization ratio (weight basis): St / CMA / i-BA / GMA / AA = 25/25/25/5/20
In the same manner as in Synthesis Example 1, 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).
　（合成例４）感光性成分Ｆ－１
　共重合比率（重量基準）：Ｓｔ／ＣＭＡ／i－ＢＡ／ＧＭＡ／ＡＡ＝４０／１０／３０／５／１５
　合成例１と同様にスチレン４０ｇ、シクロメタクリレート１０ｇ、イソブチルアクリレート３０ｇ、アクリル酸１５ｇにグリシジルメタクリレートを５ｇ付加した感光性成分Ｆ－１を得た。得られた感光性成分Ｆ－１の酸価は１０５ｍｇＫＯＨ／ｇ、式（１）より求めたガラス転移温度は６５．５℃であった。 (Synthesis Example 4) Photosensitive component F-1
Copolymerization ratio (weight basis): St / CMA / i-BA / GMA / AA = 40/10/30/5/15
In the same manner as in Synthesis Example 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.
　（合成例５）感光性成分Ｆ－２
　共重合比率（重量基準）：Ｓｔ／ＣＭＡ／i－ＢＡ／ＧＭＡ／ＡＡ＝１５／５０／１５／５／１５
　合成例１と同様にスチレン１５ｇ、シクロメタクリレート５０ｇ、イソブチルアクリレート１５ｇ、アクリル酸１５ｇにグリシジルメタクリレートを５ｇ付加した感光性成分Ｆ－２を得た。得られた感光性成分Ｆ－２の酸価は１００ｍｇＫＯＨ／ｇ、式（１）より求めたガラス転移温度は－１０．２℃であった。
・光重合開始剤（Ｃ）
ＩＲＧＡＣＵＲＥ　９０７（商品名、チバジャパン株式会社製）
ＩＲＧＡＣＵＲＥ　ＯＸＥ－０１（商品名、チバジャパン株式会社製）
・導電性フィラー（Ｄ）
表２に記載の材料、平均粒子径のものを用いた。なお、平均粒子径は以下の方法により求めた。
＜平均粒子径の測定＞
導電性フィラー（Ｄ）の平均粒子径は、ＨＯＲＩＢＡ社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。
・酸発生剤（Ｅ）
サンエイドＳＩ－１１０（商品名、三新化学工業株式会社製）
・全塩素含有量が３００ｐｐｍ以上である化合物（Ｆ）
エポキシエステル８０ＭＦＡ（共栄社化学株式会社製、全塩素濃度３００ｐｐｍ以上）
＜導電性フィラー（Ｄ）を除く全固形分量における全塩素含有量の測定方法＞
本発明の感光性導電ペーストをテーブルトップ遠心機２４２０（商品名、久保田商事株式会社製）に５０ｇいれ、３０００ｒｐｍで３０分間遠心分離を行い、上澄み溶液を１５０℃で１０時間乾燥させて得られたものを溶剤で１００倍に希釈し、固層抽出用カートリッジGL-PakPLS-3（ＧＬサイエンス社製）でろ過したろ液について塩素・硫黄分析装置ＴＯＸ－２１００Ｈ（三菱アナリテック社製）を用いて全塩素含有量を測定した。導電性フィラー（Ｄ）を除く全固形分量については、本発明の感光性導電ペーストを１５０℃で１０時間乾燥させたものを下記の条件でＴＧ測定して得られた重量減少率の値を用いて求めた。 (Synthesis Example 5) Photosensitive component F-2
Copolymerization ratio (weight basis): St / CMA / i-BA / GMA / AA = 15/50/15/5/15
In the same manner as in Synthesis Example 1, 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.
・ Photopolymerization initiator (C)
IRGACURE 907 (trade name, manufactured by Ciba Japan Co., Ltd.)
IRGACURE OXE-01 (trade name, manufactured by Ciba Japan Co., Ltd.)
・ Conductive filler (D)
The materials listed in Table 2 and those having an average particle size were used. The average particle size was determined by the following method.
<Measurement of average particle diameter>
The average particle size of the conductive filler (D) was measured by a dynamic light scattering particle size distribution meter manufactured by HORIBA.
・ Acid generator (E)
Sun-Aid SI-110 (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.)
-Compound (F) having a total chlorine content of 300 ppm or more
Epoxy ester 80MFA (Kyoeisha Chemical Co., Ltd., total chlorine concentration 300ppm or more)
<Measurement method of total chlorine content in total solid content excluding conductive filler (D)>
50 g of the photosensitive conductive paste of the present invention was placed in a table top centrifuge 2420 (trade name, manufactured by Kubota Shoji Co., Ltd.), centrifuged at 3000 rpm for 30 minutes, and the supernatant solution was dried at 150 ° C. for 10 hours. 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. For the total solid content excluding the conductive filler (D), 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.
　　　　　装置：ＴＧ－５０／５１Ｈ（商品名、株式会社島津製作所社製）
　　　　　温度：６００℃１時間保持
昇温速度：５℃／min
雰囲気：大気
・溶剤：γ－ブチロラクトン（三菱ガス化学株式会社製）
　実施例１
　１００ｍｌクリーンボトルに感光性成分Ｂ－１を２０ｇ、Ｎ－ｎ－ブトキシメチルアクリルアミドを１２ｇ、光重合開始剤ＯＸＥ－０１（チバジャパン株式会社製）を４ｇ、酸発生剤ＳＩ－１１０（三新化学工業株式会社製）を０．６ｇ、γ－ブチロラクトン（三菱ガス化学株式会社製）を１０ｇいれ、“あわとり練太郎”（商品名ＡＲＥ－３１０、株式会社シンキー社製）で混合し、感光性樹脂溶液４６．６ｇ（固形分７８．５重量％）を得た。得られた感光性樹脂溶液８．０ｇと平均粒子径２μｍのＡｇ粒子を４２．０ｇ混ぜ合わせ、３本ローラー“ＥＸＡＫＴ　Ｍ－５０”（商品名、ＥＸＡＫＴ社製）を用いて混練し、５０ｇの感光性導電ペーストを得た。 Apparatus: 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: γ-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 γ-butyrolactone (Mitsubishi Gas Chemical Co., Ltd.) (10 g) are mixed with “Awatori Nertaro” (trade name ARE-310, manufactured by Shinky Co., Ltd.). 46.6 g of resin solution (78.5 wt% solid content) was obtained. 8.0 g of the obtained photosensitive resin solution and 42.0 g of Ag particles having an average particle diameter of 2 μm were mixed, kneaded using a three-roller “EXAKT M-50” (trade name, manufactured by EXAKT), and 50 g A photosensitive conductive paste was obtained.
　得られたペーストをスクリーン印刷で膜厚５０μｍのポリイミドフィルム上に塗布し、乾燥オーブンで１００℃、１０分でプリベークを行った。その後、露光装置“ＰＥＭ－６Ｍ”（商品名、ユニオン光学（株）製）を用いて露光量７０ｍＪ／ｃｍ２（波長３６５ｎｍ換算）で全線露光を行い、０．５％Ｎａ２ＣＯ３溶液で１分間浸漬現像を行い、超純水でリンス後、乾燥オーブンで２００℃、１時間キュアを行った。パターン加工された導電パターンの膜厚は１０μｍであった。導電パターンのラインアンドスペース（Ｌ／Ｓ）パターンを光学顕微鏡により確認したところ、Ｌ／Ｓが２０／２０μｍまでパターン間残渣、パターン剥がれがなく、良好にパターン加工されていることを確認した。そして導電パターンの比抵抗率を測定したところ７．３×１０－５Ωｃｍであった。また屈曲性についても試験後クラックや断線などが生じておらず良好な結果が得られた。 The obtained paste was applied onto a polyimide film having a thickness of 50 μm 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 μm. When the line and space (L / S) pattern of the conductive pattern was confirmed with an optical microscope, it was confirmed that there was no pattern residue and pattern peeling until L / S was 20/20 μm, and the pattern was satisfactorily processed. When the specific resistivity of the conductive pattern was measured, it was 7.3 × 10 −5 Ωcm. As for the flexibility, good results were obtained with no cracks or disconnection after the test.
　実施例２～９
　表２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３に示した。
比較例１～３
　表２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３に示した。 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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Ａ　透光部
Ｂ、Ｃ　サンプル短辺
Ｄ　導電パターン
Ｅ　ポリイミドフィルム A Translucent part B, C Sample short side D Conductive pattern E Polyimide film

Claims (12)

  1. アルコキシ基を有する化合物（Ａ）、不飽和二重結合を有し、ガラス転移温度が５～４０℃の範囲内である感光性成分（Ｂ）、光重合開始剤（Ｃ）、および導電性フィラー（Ｄ）を含むことを特徴とする感光性導電ペースト。 Compound (A) having alkoxy group, photosensitive component (B) having unsaturated double bond and glass transition temperature in the range of 5 to 40 ° C., photopolymerization initiator (C), and conductive filler A photosensitive conductive paste comprising (D).
  2. 前記不飽和二重結合を有し、ガラス転移温度が５～４０℃の範囲内である感光性成分（Ｂ）のガラス転移温度が１０～３０℃の範囲内である請求項１記載の感光性導電ペースト。 The photosensitive property according to claim 1, wherein the photosensitive component (B) having the unsaturated double bond and having a glass transition temperature in the range of 5 to 40 ° C has a glass transition temperature in the range of 10 to 30 ° C. Conductive paste.
  3. 前記不飽和二重結合を有し、ガラス転移温度が５～４０℃の範囲内である感光性成分（Ｂ）の酸価が５０～２００ｍｇＫＯＨ／ｇの範囲内である請求項１～２のいずれかに記載の感光性導電ペースト。 The acid value of the photosensitive component (B) having the unsaturated double bond and having a glass transition temperature in the range of 5 to 40 ° C is in the range of 50 to 200 mgKOH / g. A photosensitive conductive paste according to claim 1.
  4. 前記不飽和二重結合を有し、ガラス転移温度が５～４０℃の範囲内である感光性成分（Ｂ）の酸価が８０～１５０ｍｇＫＯＨ／ｇの範囲内である請求項１～３のいずれかに記載の感光性導電ペースト。 The acid value of the photosensitive component (B) having an unsaturated double bond and having a glass transition temperature in the range of 5 to 40 ° C is in the range of 80 to 150 mgKOH / g. A photosensitive conductive paste according to claim 1.
  5. 前記光重合開始剤（Ｃ）が分子内にベンゾイル骨格を含むことを特徴とする請求項１～４のいずれかに記載の感光性導電ペースト。 The photosensitive conductive paste according to claim 1, wherein the photopolymerization initiator (C) contains a benzoyl skeleton in the molecule.
  6. 前記光重合開始剤（Ｃ）が１，２－オクタンジオン，１－[４－(フェニルチオ)－，２－(O－ベンゾイルオキシム)]、２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド、ビス(２，４，６－トリメチルベンゾイル)－フェニルフォスフィンオキサイド、ビス(２，４，６－トリメチルベンゾイル)－フェニルフォスフィンオキサイド、またはエタノン，１－[９－エチル－６－２（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル]－，１－(O－アセチルオキシム)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。 The photopolymerization initiator (C) is 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, or ethanone, 1- [9-ethyl-6-2 (2 The photosensitive conductive paste according to claim 1, which is -methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
  7. さらに酸発生剤（Ｅ）を含有する請求項１～６のいずれかに記載の感光性導電ペースト。 The photosensitive conductive paste according to any one of claims 1 to 6, further comprising an acid generator (E).
  8. 前記酸発生剤（Ｅ）がスルホニウム塩である請求項７に記載の感光性導電ペースト。 The photosensitive conductive paste according to claim 7, wherein the acid generator (E) is a sulfonium salt.
  9. さらに全塩素含有量が３００ｐｐｍ以上である化合物（Ｆ）を含むことを特徴とする請求項１～８のいずれかに記載の感光性導電ペースト。 The photosensitive conductive paste according to any one of claims 1 to 8, further comprising a compound (F) having a total chlorine content of 300 ppm or more.
  10. 前記全塩素含有量が３００ｐｐｍ以上である化合物（Ｆ）が不飽和二重結合含有化合物もしくはグリシジル基含有化合物であることを特徴とする請求項９に記載の感光性導電ペースト。 The photosensitive conductive paste according to claim 9, wherein the compound (F) having a total chlorine content of 300 ppm or more is an unsaturated double bond-containing compound or a glycidyl group-containing compound.
  11. 請求項１～１０のいずれかに記載の感光性導電ペーストの導電性フィラー（Ｄ）を除く全固形分量における全塩素含有量が１００ｐｐｍ以上であることを特徴とする感光性導電ペースト。 A photosensitive conductive paste characterized in that the total chlorine content in the total solid content excluding the conductive filler (D) of the photosensitive conductive paste according to any one of claims 1 to 10 is 100 ppm or more.
  12. 請求項１～１１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１３０℃以上４００℃以下の温度でキュアすることを特徴とする導電パターンの製造方法。 A photosensitive conductive paste according to any one of claims 1 to 11, which is coated on a substrate, dried, exposed and developed, and then cured at a temperature of 130 ° C to 400 ° C. Production method.
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JP2011180580A (en) * 2010-02-02 2011-09-15 Toray Ind Inc Photosensitive paste for forming organic-inorganic composite conductive pattern and method for producing organic-inorganic composite conductive pattern
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JP2013249467A (en) * 2012-05-31 2013-12-12 Lg Chem Ltd New polymer and coloring composition including the same
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