WO2017159445A1 - 感光性導電ペーストおよび導電パターン付基板の製造方法 - Google Patents

感光性導電ペーストおよび導電パターン付基板の製造方法 Download PDF

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WO2017159445A1
WO2017159445A1 PCT/JP2017/008908 JP2017008908W WO2017159445A1 WO 2017159445 A1 WO2017159445 A1 WO 2017159445A1 JP 2017008908 W JP2017008908 W JP 2017008908W WO 2017159445 A1 WO2017159445 A1 WO 2017159445A1
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Prior art keywords
compound
conductive paste
photosensitive
photosensitive conductive
conductive pattern
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PCT/JP2017/008908
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English (en)
French (fr)
Japanese (ja)
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麻里恵 小山
創 水口
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東レ株式会社
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Priority to KR1020187019339A priority Critical patent/KR20180121875A/ko
Priority to CN201780012523.XA priority patent/CN108700806A/zh
Priority to JP2017514922A priority patent/JP6566027B2/ja
Publication of WO2017159445A1 publication Critical patent/WO2017159445A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a photosensitive conductive paste capable of forming a fine conductive pattern and a method for manufacturing a substrate with a conductive pattern using the photosensitive conductive paste.
  • the present invention provides a photosensitive conductive paste that is excellent in straightness and that forms a fine conductive pattern and exhibits high conductivity.
  • the present invention is a photosensitivity containing conductive particles (A), a compound (B) having an unsaturated double bond, a photopolymerization initiator (C), and a compound (D) having a hydroxypyridine skeleton in one molecule. It is a conductive paste.
  • the compound (D) having a hydroxypyridine skeleton in one molecule is a compound having a methylol group.
  • the content of the compound (D) having a hydroxypyridine skeleton in one molecule is 100 parts by mass of the compound (B) having the unsaturated double bond. Is 0.3 to 10 parts by mass.
  • thermosetting resin (E) is contained.
  • thermosetting resin (E) is an epoxy resin having an epoxy equivalent of 150 to 500 g / equivalent.
  • a substrate with a conductive pattern can be produced by applying the above-mentioned photosensitive conductive paste on a substrate and curing it at a temperature of 100 to 300 ° C.
  • the photosensitive conductive paste of the present invention can be suitably used for manufacturing conductive patterns such as peripheral wiring for touch panels.
  • the photosensitive conductive paste of the present invention comprises a conductive particle (A), a compound (B) having an unsaturated double bond, a photopolymerization initiator (C), a compound (D) having a hydroxypyridine skeleton in one molecule, Containing.
  • the conductive pattern obtained from the photosensitive conductive paste of the present invention is a composite of an organic component and an inorganic component, and the conductive particles (A) are brought into contact with each other by curing shrinkage during thermal curing. Conductivity is expressed.
  • the conductive particles (A) contained in the photosensitive conductive paste of the present invention include at least one conductive material selected from silver, gold, copper, platinum, lead, tin, nickel, aluminum, tungsten, molybdenum, chromium, titanium, and indium.
  • the conductive filler is preferably included, and these conductive fillers can be used alone, as an alloy, or as a mixed powder.
  • conductive particles obtained by coating the surfaces of insulating particles such as resins and inorganic oxides or conductive particles with the above-described components can be used as well.
  • silver, gold or copper is preferable from the viewpoint of conductivity, and silver is more preferably used from the viewpoint of cost and stability.
  • the aspect ratio which is a value obtained by dividing the major axis length by the minor axis length, is preferably 1.0 to 3.0, and preferably 1.0 to 2.0. Is a more preferred embodiment.
  • the aspect ratio of the conductive particles (A) is 1.0 or more, the contact probability between the conductive particles (A) is further increased.
  • the conductive particles (A) have an aspect ratio of 2.0 or less, exposure light is not easily shielded when a wiring is formed by a photolithography method, and the development margin can be widened.
  • the conductive particles (A) were observed at a magnification of 15000 times using a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 conductive particles were randomly selected.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the primary particles of the active particles are selected, the major axis length and the minor axis length of each are measured, and the aspect ratio is obtained from the average value of both.
  • the particle size of the conductive particles (A) is preferably 0.05 to 5.0 ⁇ m, more preferably 0.1 to 2.0 ⁇ m.
  • the particle size of the conductive particles (A) is 0.05 ⁇ m or more, the interaction between the particles is weak, and the dispersed state of the conductive particles (A) in the paste is easily maintained.
  • the particle size of the conductive particles (A) is 5.0 ⁇ m or less, the surface smoothness, pattern accuracy, and dimensional accuracy of the manufactured conductive pattern can be improved.
  • the particle size of the conductive particles (A) contained in the photosensitive conductive paste is observed with an electron microscope, the primary particles of 20 conductive particles are selected at random, and the maximum width of each is measured. It calculates by calculating
  • the content of the conductive particles (A) is preferably 60 to 95% by mass, more preferably 75 to 90% by mass with respect to the total solid content in the conductive paste.
  • the content of the conductive particles (A) with respect to the total solid content is 60% by mass or more, the contact probability between the conductive particles (A) during curing is improved, and the resistivity and the disconnection probability of the manufactured conductive pattern are improved. Becomes lower.
  • the content of the conductive particles (A) with respect to the total solid content is 95% by mass or less, the translucency of the coating film is improved in the exposure step, and fine patterning is facilitated.
  • the total solid content means all components of the photosensitive conductive paste excluding the solvent.
  • Examples of the compound (B) having an unsaturated double bond contained in the photosensitive conductive paste of the present invention include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ⁇ -methylstyrene, and chloromethyl.
  • Examples thereof include styrenes such as styrene or hydroxymethylstyrene, acrylic monomers, acrylic copolymers, epoxy carboxylate compounds, and 1-vinyl-2-pyrrolidone.
  • acrylic monomers examples include acrylic acid, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, n-butyl acrylate, iso-butyl acrylate, iso-propane acrylate, glycidyl acrylate, butoxytriethylene glycol acrylate, and dicyclopentanyl.
  • the acrylic copolymer refers to a copolymer containing an acrylic monomer in the monomer used, that is, a copolymer component.
  • the alkali-soluble acrylic copolymer having a carboxyl group can be obtained by using an unsaturated acid such as an unsaturated carboxylic acid as a monomer.
  • unsaturated acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid or vinyl acetate, and acid anhydrides thereof.
  • the acid value of the obtained acrylic copolymer can be adjusted depending on the amount of the unsaturated acid used.
  • the epoxycarboxylate compound refers to a compound that can be synthesized using an epoxy compound and a carboxyl compound having an unsaturated double bond as starting materials.
  • examples of the epoxy compound that can be a starting material include glycidyl ethers, alicyclic epoxy resins, glycidyl esters, glycidyl amines, or epoxy resins.
  • the acid value of the epoxycarboxylate compound can be adjusted by reacting the epoxycarboxylate compound with the polybasic acid anhydride.
  • the polybasic acid anhydride include succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyltetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Examples include trimellitic anhydride and maleic anhydride.
  • an epoxy carboxylate compound has by reacting the carboxyl group which the epoxy carboxylate compound made to react with the above-mentioned polybasic acid anhydride has, and the compound which has unsaturated double bonds, such as glycidyl (meth) acrylate,
  • the amount of sex unsaturated double bonds can be adjusted.
  • Urethane can be obtained by reacting the hydroxy group of the epoxycarboxylate compound with a diisocyanate compound.
  • the diisocyanate compound include hexamethylene diisocyanate, tetramethylxylene diisocyanate, naphthalene-1,5-diisocyanate, tridenic diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, allyl cyanide diisocyanate, and norbornane diisocyanate.
  • the acid value of the compound (B) having an unsaturated double bond is preferably 30 to 250 mgKOH / g in order to optimize alkali solubility.
  • the acid value of the compound (B) having an unsaturated double bond is 30 mgKOH / g or more, the solubility of the soluble part can be suppressed.
  • the acid value of the compound (B) having an unsaturated double bond is 250 mgKOH / g or less, the development allowable width can be maintained.
  • the acid value of the compound (B) having an unsaturated double bond can be measured according to JIS K 0070 (1992).
  • Examples of the photopolymerization initiator (C) contained in the photosensitive conductive paste of the present invention include benzophenone, methyl O-benzoylbenzoate, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Diethylamino) benzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl ketone, benzophenone derivatives such as fluorenone, pt-butyldichloroacetophenone, 4-azidobenzalacetophenone, 2,2′-di Acetophenone derivatives such as ethoxyacetophenone, thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl, benzyldimethyl ketal, benz
  • ⁇ -aminoalkylphenone compounds 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phen Phosphine oxide compounds such as nylphosphine oxide, aromatic sulfonyl chloride compounds such as naphthalenesulfonyl chloride and quinolinesulfonyl chloride, anthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, ⁇ -chloroanthraquinone, anthrone, benzanthrone , Dibenzosuberone, methyleneanthrone, 2,6-bis (p-azidobenzylidene) cyclohexanone, 6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2,6-bis (p-azidobenzylidene) cyclohex
  • the content of the photopolymerization initiator (C) is preferably 0.05 to 30 parts by mass and preferably 1 to 10 parts by mass with respect to 100 parts by mass of the compound (B) having an unsaturated double bond. Is more preferable.
  • the content of the photopolymerization initiator (C) is 0.05 parts by mass or more with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, the cured density of the exposed part increases, The remaining film rate can be increased.
  • the content of the photopolymerization initiator (C) is 30 parts by mass or less with respect to 100 parts by mass of the compound (B) having an unsaturated double bond
  • the content of the photopolymerization initiator (C) is the upper part of the coating film obtained by applying the conductive paste. Excessive light absorption by the photopolymerization initiator (C) is suppressed. As a result, a decrease in adhesion with the substrate due to the manufactured conductive pattern having an inversely tapered shape is suppressed.
  • the photosensitive conductive paste of the present invention can contain a sensitizer together with the photopolymerization initiator (C).
  • sensitizer examples include 2,4-diethylthioxanthone, isopropylthioxanthone, 2,3-bis (4-diethylaminobenzal) cyclopentanone, 2,6-bis (4-dimethylaminobenzal) cyclohexanone, 2 , 6-bis (4-dimethylaminobenzal) -4-methylcyclohexanone, Michler's ketone, 4,4-bis (diethylamino) benzophenone, 4,4-bis (dimethylamino) chalcone, 4,4-bis (diethylamino) chalcone P-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylvinylene) isonaphthothiazole, 1,3-bis (4-dimethylaminophenylvinylene) isonaphthothiazole,
  • the content of the sensitizer is preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the compound (B) having an unsaturated double bond.
  • the content of the sensitizer is 0.05 parts by mass or more with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, the photosensitivity is improved.
  • the content of the sensitizer is 10 parts by mass or less with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, excess light on the upper part of the coating film obtained by applying the conductive paste. Absorption is suppressed. As a result, a decrease in adhesion with the substrate due to the manufactured conductive pattern having an inversely tapered shape is suppressed.
  • Examples of the compound (D) having a hydroxypyridine skeleton in one molecule contained in the photosensitive conductive paste of the present invention include 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,4-dihydroxypyridine, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,8-dihydroxyquinoline, 5-hydroxy-2-methylpyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methylpyridine, 2- Hydroxy-6-methylpyridine, 2,4-dihydroxy-6-methylpyridine, 2-ethyl-3-hydroxy-6-methylpyridine, 4-bromo-2-hydroxypyridine, 4-chloro-2-hydroxypyridine, 2 -Hydroxy-5-iodopyridine, 3-hydroxyisoquinori , 2-quinolinol, 3-quinolinol, 2-methyl-4-quinolinol, pyridoxal-5-phosphate, citrazinic acid, 6-hydroxy nicotinic acid, and salts thereof.
  • pyridoxine having a methylol group 4-deoxypyridoxine, pyridoxal, pyridoxamine, 4-pyridoxy acid, isopyridoxal, 2-hydroxymethyl-3-pyridinol, 2-hydroxymethyl-6-methyl-3-pyridinol, 2,6 -Bis (hydroxymethyl) -3-pyridinol, ginkotoxin, pyridoxine dicaprylate, pyridoxal oxime, 6- (hydroxymethyl) -3,4-pyridinediol, 2-bromo-6- (hydroxymethyl) -3-pyridinol, 2,5-dichloro-6- (hydroxymethyl) -3-pyridinol, 2-chloro-6- (hydroxymethyl) -4-iodo-3-pyridinol, 3- (hydroxymethyl) -6-methyl-4-quinolinol , Pyridoxine-3,4- Palmitate, and these salts, since the reaction-inhibiting effect of the organic component not too strong
  • the content of the compound (D) having a hydroxypyridine skeleton in one molecule is preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the compound (B) having an unsaturated double bond. It is more preferable to contain 5 to 5 parts by weight.
  • the content of the compound (D) having a hydroxypyridine skeleton in one molecule is 0.3 parts by mass or more with respect to 100 parts by mass of the compound (B) having an unsaturated double bond, photoradical reaction at the time of exposure
  • the straightness of the conductive pattern is improved, and since the curing of the resin component of the conductive pattern does not proceed excessively before the curing, the conductive particles (A )
  • the contact probability between each other increases, and the specific resistance value decreases.
  • the photoradical reaction is not excessively suppressed. Therefore, fine patterning is possible.
  • the photosensitive conductive paste of the present invention can contain a thermosetting resin (E).
  • the thermosetting resin (E) include epoxy resins, phenol resins, urea resins, melamine resins, unsaturated polyester resins, silicon resins, and polyurethanes.
  • an epoxy resin is preferable, and an epoxy resin having an epoxy equivalent of 150 to 500 g / equivalent is preferable among the epoxy resins.
  • the epoxy equivalent of the epoxy resin By setting the epoxy equivalent of the epoxy resin to 150 g / equivalent or more, it is possible to obtain a photosensitive conductive paste having a storage stability of the coating film.
  • the epoxy equivalent of the epoxy resin By setting the epoxy equivalent of the epoxy resin to 500 g / equivalent or less, a conductive pattern having high adhesion to various substrates such as a resin film and a glass substrate can be obtained.
  • the epoxy equivalent refers to the mass of a resin containing 1 equivalent of an epoxy group, and is obtained by dividing the molecular weight obtained from the structural formula by the number of epoxy groups contained in the structure.
  • the content of the epoxy resin is preferably in the range of 1 to 100 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the compound (B) having an unsaturated double bond.
  • the content of the epoxy resin is 1 part by mass or more with respect to 100 parts by weight of the compound (B) having an unsaturated double bond, the effect of improving the adhesion is easily exhibited, and the unsaturated double bond
  • a photosensitive conductive paste with particularly high storage stability of the coating film can be obtained.
  • the epoxy resin preferably has an epoxy equivalent in the range of 150 to 500 g / equivalent, and more preferably in the range of 200 to 500 g / equivalent.
  • Specific examples include ethylene glycol-modified epoxy resins, bisphenol A type epoxy resins, brominated epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins, alicyclic epoxy resins, glycidyl amine type epoxy resins, glycidyl ether type epoxy resins. And heterocyclic epoxy resins.
  • the photosensitive conductive paste of the present invention can 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.
  • the photosensitive conductive paste of the present invention is a non-photosensitive polymer having no unsaturated double bond in the molecule, plasticizer, leveling agent, surfactant, silane coupling, as long as the desired properties are not impaired. Additives such as agents, antifoaming agents, and pigments can be included.
  • non-photosensitive polymer examples include polyethylene terephthalate, polyimide precursor, and closed ring polyimide.
  • plasticizer examples include dibutyl phthalate, dioctyl phthalate, polyethylene glycol, and glycerin.
  • leveling agent examples include a special vinyl polymer and a special acrylic polymer.
  • silane coupling agent examples include methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyl.
  • a trimethoxysilane is mentioned.
  • the photosensitive conductive paste of the present invention is produced, for example, using a dispersing machine or a kneader such as a three roller mill, a ball mill or a planetary ball mill.
  • the photosensitive conductive paste of the present invention is applied on a substrate, dried, exposed and developed, and then cured at a temperature of 100 to 300 ° C.
  • a coated film is obtained by coating the photosensitive conductive paste of the present invention on a substrate.
  • a substrate to which the photosensitive conductive paste is applied for example, a polyethylene terephthalate film (hereinafter referred to as PET film), a polyimide film, a polyester film, an aramid film, an epoxy resin substrate, a polyetherimide resin substrate, a polyetherketone resin substrate, Examples include a polysulfone-based resin substrate, a glass substrate, a silicon wafer, an alumina substrate, an aluminum nitride substrate, a silicon carbide substrate, a decorative layer forming substrate, and an insulating layer forming substrate.
  • a method for applying the photosensitive conductive paste of the present invention to a substrate for example, spin coating using a spinner, spray coating, roll coating, screen printing or blade coater, die coater, calendar coater, meniscus coater or bar coater is used. Applied.
  • the film thickness of the obtained coating film can be appropriately determined according to the coating method or the total solid content concentration or viscosity of the photosensitive conductive paste, but the film thickness after drying should be 0.1 to 50 ⁇ m. Is preferred.
  • the film thickness can be measured by using a stylus step meter such as Surfcom (registered trademark) 1400 (manufactured by Tokyo Seimitsu Co., Ltd.). More specifically, the film thicknesses at three randomly selected positions are respectively measured with a stylus type step gauge (measurement length: 1 mm, scanning speed: 0.3 mm / second), and an average value thereof is obtained. To calculate.
  • the coating film is dried to evaporate the solvent.
  • Examples of the method for drying the coating film to volatilize and remove the solvent include heat drying and vacuum drying using an oven, a hot plate, infrared rays, or the like.
  • the heating temperature is preferably 50 to 180 ° C., and the heating time is preferably 1 minute to several hours.
  • the coating film after drying is exposed by a photolithography method through an arbitrary pattern forming mask.
  • i-line (365 nm), h-line (405 nm) or g-line (436 nm) of a mercury lamp is preferably used.
  • the coated film after exposure is developed using a developer, and unexposed portions are dissolved and removed to obtain a desired pattern.
  • the developer used for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, and dimethyl acetate.
  • Examples include an aqueous solution of aminoethyl, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, or hexamethylenediamine.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or ⁇ -butyrolactone, alcohols such as methanol, ethanol or isopropanol, ethyl lactate
  • esters such as propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone or methyl isobutyl ketone, and a surfactant can be added.
  • Examples of the developer for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoryl
  • Examples thereof include polar solvents such as amides or mixed solutions of these polar solvents with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, and ethyl carbitol.
  • a development method for example, a method of spraying a developer onto the coating film surface while the substrate is left standing or rotating, a method of immersing the substrate in the developer, and an ultrasonic wave while immersing the substrate in the developer The method of applying is mentioned.
  • the conductive pattern obtained by development can be rinsed with a rinse solution.
  • a rinse solution examples include water or an aqueous solution in which an alcohol such as ethanol or isopropyl alcohol or an ester such as ethyl lactate or propylene glycol monomethyl ether acetate is added to water.
  • the obtained conductive pattern is cured at a temperature of 100 to 300 ° C.
  • the curing temperature is preferably 120 to 180 ° C.
  • the curing temperature is less than 100 ° C., the volume shrinkage of the resin component is not increased and the specific resistance is not sufficiently lowered.
  • the curing temperature exceeds 300 ° C., it is difficult to produce a conductive pattern on a material such as a substrate having low heat resistance.
  • the obtained conductive pattern for example, heating and drying using an oven, an inert oven or a hot plate, electromagnetic waves such as an ultraviolet lamp, an infrared heater, a halogen heater or a xenon flash lamp, or heating and drying using a microwave, or And vacuum drying.
  • electromagnetic waves such as an ultraviolet lamp, an infrared heater, a halogen heater or a xenon flash lamp, or heating and drying using a microwave, or And vacuum drying.
  • the conductive pattern obtained by using the photosensitive conductive paste of the present invention is suitably used for a touch panel, a multilayer ceramic capacitor, a multilayer inductor, a solar cell, etc. More preferably used for wiring.
  • the photosensitive conductive paste was applied onto a PET film so that the film thickness after drying was 4 ⁇ m, and dried in a drying oven at 100 ° C. for 5 minutes.
  • a photomask having a group of straight lines arranged in a certain line and space (hereinafter referred to as L / S), that is, a translucent pattern as one unit, and 10 types of units having different L / S values.
  • the coated film after drying was exposed and developed to obtain 10 types of patterns having different L / S values. Thereafter, the ten patterns obtained were each cured in a drying oven at a temperature of 140 ° C. for 30 minutes to obtain ten types of conductive patterns having different L / S values.
  • the L / S value of each unit of the photomask is such that the line width L ( ⁇ m) / interval S ( ⁇ m) is 250/250, 100/100, 50/50, 40/40, 30/30, 25 / 25, 20/20, 15/15, 10/10, and 7/7.
  • the obtained conductive pattern was observed with an optical microscope. A conductive pattern having a minimum L / S value with no residue between the patterns and no pattern peeling was confirmed.
  • the L / S value was defined as a developable L / S value.
  • an exposure apparatus (PEM-6M; manufactured by Union Optics Co., Ltd.) is used to perform full-line exposure at an exposure amount of 150 mJ / cm 2 (wavelength 365 nm conversion), and development is performed on a 0.2% by mass Na 2 CO 3 solution.
  • the substrate was immersed for 30 seconds and then rinsed with ultrapure water.
  • the photosensitive conductive paste was applied onto a PET film so that the film thickness after drying was 4 ⁇ m, and the coated film was dried in a drying oven at a temperature of 100 ° C. for 5 minutes.
  • the coated film after drying was exposed and developed through a photomask having a translucent pattern A shown in FIG. 2 to obtain a conductive pattern.
  • the obtained conductive pattern was cured in a drying oven at a temperature of 140 ° C. for 30 minutes to obtain a conductive pattern for specific resistance measurement.
  • the obtained conductive pattern had a line width of 20 ⁇ m and a line length of 80 mm.
  • IRGACURE registered trademark
  • OXE01 Ciba Japan Co., Ltd., oxime compound
  • IRGACURE registered trademark 369 (manufactured by Ciba Japan Co., Ltd., ⁇ -aminoalkylphenone compound) (hereinafter referred to as IC369).
  • Epoxy resin (E-1) JER (registered trademark) 828 (epoxy equivalent 188) manufactured by Mitsubishi Chemical Corporation
  • Example 1 In a 100 mL clean bottle, put 10.0 g of compound (B-1), 0.50 g of OXE01, 5.0 g of DMEA and 0.5 g of 2-hydroxypyridine, and rotate and revolve vacuum mixer “Awatori Rentaro” The mixture was mixed with ARE-310 (registered trademark; manufactured by Shinkey Co., Ltd.) to obtain 16.0 g of a resin solution (solid content: 68.8% by mass).
  • ARE-310 registered trademark; manufactured by Shinkey Co., Ltd.
  • the developable L / S value which is an evaluation index of patterning property, was 15/15, and it was confirmed that favorable pattern processing was performed.
  • the length of the protrusion of the conductive pattern was 2.7 ⁇ m, and it was confirmed that the straightness was “good”.
  • the specific resistance of the conductive pattern was 6.0 ⁇ 10 ⁇ 5 ⁇ cm. The evaluation results are shown in Table 2.
  • Example 2 A photosensitive conductive paste having the composition shown in Table 1 was produced in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • the photosensitive conductive paste of the present invention can be suitably used for manufacturing conductive patterns such as peripheral wiring for touch panels.

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  • Organic Chemistry (AREA)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Human Computer Interaction (AREA)
  • Laminated Bodies (AREA)
  • Materials For Photolithography (AREA)
  • Non-Insulated Conductors (AREA)
  • Conductive Materials (AREA)
  • Position Input By Displaying (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
PCT/JP2017/008908 2016-03-17 2017-03-07 感光性導電ペーストおよび導電パターン付基板の製造方法 WO2017159445A1 (ja)

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CN201780012523.XA CN108700806A (zh) 2016-03-17 2017-03-07 感光性导电糊剂及带导电图案的基板的制造方法
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