CN1058741C - 水性含银组合物 - Google Patents
水性含银组合物 Download PDFInfo
- Publication number
- CN1058741C CN1058741C CN95121553A CN95121553A CN1058741C CN 1058741 C CN1058741 C CN 1058741C CN 95121553 A CN95121553 A CN 95121553A CN 95121553 A CN95121553 A CN 95121553A CN 1058741 C CN1058741 C CN 1058741C
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- weight
- coating composition
- described coating
- polymer binder
- silver powder
- Prior art date
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000004332 silver Substances 0.000 title description 23
- 229910052709 silver Inorganic materials 0.000 title description 23
- 239000008199 coating composition Substances 0.000 claims abstract description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002492 water-soluble polymer binding agent Substances 0.000 claims abstract description 6
- 229920005596 polymer binder Polymers 0.000 claims description 28
- 239000002491 polymer binding agent Substances 0.000 claims description 28
- 239000010687 lubricating oil Substances 0.000 claims description 20
- 238000005245 sintering Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- 239000013530 defoamer Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000005388 borosilicate glass Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- -1 polysiloxane copolymer Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 230000007704 transition Effects 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229920006243 acrylic copolymer Polymers 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 2
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 150000002191 fatty alcohols Chemical group 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 3
- 239000004908 Emulsion polymer Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 17
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- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229920002125 Sokalan® Polymers 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 239000007921 spray Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000012855 volatile organic compound Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical class CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002169 ethanolamines Chemical class 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
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- 238000002156 mixing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920005692 JONCRYL® Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 238000000498 ball milling Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
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- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 229940098695 palmitic acid Drugs 0.000 description 1
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- 231100000614 poison Toxicity 0.000 description 1
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
-
- 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
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
- H01L23/49883—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials the conductive materials containing organic materials or pastes, e.g. for thick films
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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Abstract
本发明公开了一种含片状银粉的涂料组合物,片状银粉悬浮于以水为主的载体中,并可在电阻性或绝缘性的基底上形成一层导电金属沉积层,可广泛应用于电子工业。该涂料组合物提供了具有理想的含高银含量和低粘度的结合,适于一次高速喷涂就可达到所需涂层厚度。这种新型涂料组合物包括片状银粉、水溶性聚合物粘合剂、水及一种可充分溶于水的有机助溶剂。本涂料组合物干燥后具有良好的未烧结强度,并可在塑料或弹性体原件上涂覆一层导电层,使原件可被电镀。可选择性地加入一种烧结粘附组分,经高温焙烧使银层与陶瓷基底可以永久结合。本涂料组合物有优异的贮存稳定性,沉淀的固体经短时的和/或轻微的搅拌,就很容易再次分散。
Description
本发明涉及一种水性金属悬浮液,适用于对电阻性或绝缘性基底涂覆导电金属。
向具有电阻性和绝缘性基底的电子原件上涂覆一薄层导电金属,在工业上具有重大意义。由金属微粒分散均匀地悬浮于液态载体中构成的涂料组合物,可以用喷涂、刷涂、浸涂、滚涂或丝网印刷方法在基底上形成一层导电金属层。其中喷涂是涂覆导电金属层的优选方法,因为它不仅快而且可以在形状很复杂的原件上形成薄而均匀的沉积层。此后,涂料组合物可以在环境温度或稍高温度下干燥,再将原件在高温下焙烧,从而使金属与基底永久结合。
传统地,含银涂料组合物的液态载体中所用的溶剂主要是挥发性有机化合物(简称VOC)。基于VOC的载体存在一些缺点,如有毒、易燃甚至可能易爆。VOC原料价格昂贵而且排废花销也很大。通常,涂装过程中VOC的挥散会对周围空气造成污染。为了收集并容纳挥散出的VOC溶剂,需要昂贵的设备及工艺规程,以保证废物清理完全并减少空气污染。
尽管需要一种基于水性载体的可喷涂的含银涂料组合物,但至今仍不知如何配制这种组合物。因为银上的润滑油是配制水基涂料组合物的障碍。片状银粉一般是通过碾碎润滑的粒状银粉得到的。润滑油是确保金属微粒经碾碎形成片状粉末的关键。已发现残留在片状粉末表面的润滑油会使片状银粉具有疏水性且很难分散于水中。分散不良的片状银粉不可能被均匀地喷涂,就会在基底上形成不规则的涂层。此外,工业上常用小孔喷嘴的喷枪,分散不良的含银涂料组合物常常会堵塞喷嘴小孔。另外,为了在最少次数的高速喷涂过程中达到规定的涂层厚度,而且较佳的是一次达到,就希望组合物中银微粒浓度很高。然而,银微粒浓度过高,涂料组合物的粘度就会急剧上升,给喷涂作业带来不利影响。此外,银浓度高也易使银趋于沉淀并结成不可逆转的块。在本发明之前,还没有一种低粘度、高含银量、可喷涂的基于水性载体的涂料组合物。
因此,本发明的主要目的是提供一种安全的、利于周围环境的涂银陶瓷原件。本发明的特点在于含银涂料组合物的水性液态载体中基本不含挥发性有机化合物。本发明提供了一种利于涂覆陶瓷原件的含银涂料组合物,且无需进行安全处理或回收大量的挥发性有机物。
本发明的另一个目的是提供一种可利用常用涂装设备,也无需对现有生产工艺作出较大改动而被涂覆的含银涂料组合物。本发明的优点在于可以配制一种均匀分散的基于含润滑油的片状银粉的水性涂料组合物。本发明的特点在于涂料组合物具有最佳的低粘度和非常高片状银粉含量的联合。因此本发明的另一个优点是可以使用现有的小孔喷嘴,经高速喷涂,将含银涂料组合物一次涂覆成一层均匀的、附着牢固的金属涂层。
本发明还有一个目的是提供一种稳定的涂料组合物,在存贮过程中,片状银粉不会与液态载体分离。本发明含有能促进并保持银粉分散于水基载体中的组分。本发明的一个附加特点是:一旦有固态物沉淀,就会在轻微搅拌作用下很容易地再分散于载体中。
因此,现提供一种涂料组合物,含有:(a)约30~80%(重量)的涂有润滑油的片状银粉,所述润滑油含有至少一种直链羧酸或其盐,具有6~18个碳原子,(b)约1.5~4.5%(重量)可充分溶于水的聚合物粘合剂,(c)0~约9.5%(重量)的可充分溶于水的助溶剂,以及(d)有效溶剂量的水,所述百分数是基于涂料组合物的全部重量。
如果希望银层永久附着于适用的耐温基底,如陶瓷,则组合物中对包含任意一种能烧结粘附的组分,并且已涂覆的原件能在约600至950℃的温度下焙烧一段时间,足以激活烧结粘附性。其后,将原件冷却,使烧结粘附层固化。
本发明涉及一种可喷涂的涂料组合物,由片状银粉悬浮在水性载体中组成。此涂料组合物可喷涂于电阻性或绝缘性的基底上,然后在环境温度或稍高温度的低曙干燥步骤中排去绝大部分水。低温干燥后,片状银粉就暂时但牢固地附着于基底上。随后,可选择性地进行以下步骤:充分加热干燥的原件,烧结无机粘附组分,使银永久附着在基底上。
组分银是一种均匀分散的片状粉末,典型地生产方法是在润滑油的存在下将粒状银粉放入球磨机中研磨。适用于本发明的润滑油包括饱和及不饱和的脂肪族羧酸及盐,优选的是所述酸的碱土金属盐。这些羧酸是直链羧酸,优选的具有6~18个碳原子的一元羧酸。典型的饱和羧酸为月桂酸、软脂酸和硬脂酸,典型的不饱和羧酸为油酸、亚油酸和亚麻酸。尽管一种酸或盐可以在润滑油组合物中是主要的,但润滑油通常包括酸或盐的混合物。将润滑油溶解于醇或200#溶剂汽油后加入研磨机中。银通常被研磨成薄片状微粒,其厚度约为0.1至0.5微米,平均长度约为3至10微米,优选长度低于15微米。由于片状银粉是叠层形的,因此其微粒比粒状粉末微粒结合得更加紧密,并使片状粉末具有高的堆积密度。适用于本发明的片状银粉的振实密度,即堆积密度大于约2.0克/厘米3,优选范围是约2.5至3.5克/厘米3。相比之下,粒状银粉的振实密度约为0.8至1.5克/厘米3。本发明片状银粉的表面积约为1.1至1.8米2/克。本涂料组合物优选地含有约60至75%(重量)的片状银粉。
本涂料组合物优选地含有约1.5至4.0%(重量)的聚合物粘合剂,它使片状银粉与基底经低温干燥后牢固结合。优选的聚合物粘合剂是水可溶的丙烯酸类聚合物的水性乳液。丙烯酸类聚合物为以下单体的均聚物或共聚物:丙烯酸、甲基丙烯酸,有时还涉及如(甲基)丙烯酸、(甲基)丙烯酸的C1~C12烷基酯及这些单体的混合物。典型的丙烯酸类聚合物包括聚丙烯酸、聚甲基丙烯酸、聚甲基丙烯酸甲酯、聚硬脂酰甲基丙烯酸酯、聚甲基丙烯酸酯、聚乙基丙烯酸酯和聚丁基丙烯酸酯。丙烯酸类共聚物所用的共聚单体可带有苯乙烯或羟基官能团。
聚合物粘合剂的水乳液可用碱或胺中和至pH约为7~12,优选为8-10。中和作用引起聚合物链的伸展,从而使乳液微粒吸水膨胀并充分溶于水性介质中。加入可充分溶于水的聚合物粘合剂显著地降低了涂料组合物的粘度,从而更有利于喷涂。"可充分溶于水"是指固体材料充分溶解至与水混合成为一相的程度。可认为可溶解聚合物的羧基官能团对片状银粉分散于水性载体中起到协同作用。适用的碱和胺中和剂包括氢氧化铵、氢氧化钠、氢氧化钾、二甲氨基乙醇、单乙醇胺和吗啉,优选的是单乙醇胺。适用于本发明的粘合剂的平均分子量约在5,000至80,000之间,优选在15,000至约60,000之间。聚合物粘合剂的酸值不低于60毫克KOH/克聚合物。聚合物粘合剂的玻璃化转变温度(Tg)约在-10℃~80℃之间,优选为约25℃~60℃。重要的是本发明的聚合物粘合剂在焙烧过程中几乎能完全燃尽,因此影响高温焙烧的残余物只有极少量。典型的可商业购买的聚合物粘合剂包括S.C.Johnson公司的Joncryl142,它是一种丙烯酸类聚合物,其分子量约为48,000,酸值约为130毫克KOH/克,Tg低于约7℃;B.F.Goodrich公司的GarbosetGA1914,它是一种丙烯酸类乳液聚合物,其酸值约125,Tg约35℃;及BASF公司的Sokalon CP-45,它是一种丙烯酸/马来酸共聚物,分子量约70,000,酸值约210。Rohm及Haas公司(费城,宾西法尼亚)的产品AcrysolI-62(分子量15,000,酸值100,Tg为45℃)和AcrysolI-2426(分子量60,000,酸值115,Tg为54℃(作为聚合物粘合剂特别有效。也可使用预中和的,即溶液型商业聚合物粘合剂,如B.F.Goodrich公司的GarbosetGA1594,它是一种丙烯酸类聚合物,其Tg约28℃,酸值为65毫克KOH/克,并用二甲氨基乙醇预中和。
水,优选去离子水,以有效溶剂量存在于水性载体中,即水是主要液相组分,而且是聚合物粘合剂、助溶剂及任何水可溶的表面活性剂及消泡剂添加物的溶剂。水性载体中还含有少量可充分溶于水的有机助溶剂,该助溶剂的沸点比水高,该助溶剂可与银、聚合物粘合剂及水体系混溶,它提高了疏水性片状银粉在载体中的分散性,促进了涂料组合物的结合性及成膜性,并确定了涂料组合物的最佳粘度。已涂覆的原件经低温干燥后仍可能有一些助溶剂残留,因此助溶剂应完全燃烧,焙烧处只会留下极少量的含碳残渣。优选的是,助溶剂约占涂料组合物全部重量的0.5~8.0%(重量)。助溶剂浓度较低是优选的,为了减少挥发性有机物在涂料组合物中的含量。用于水性载体中的助溶剂包括具有2~18个碳原子的强极性的能充分溶于水的有机溶剂,包括脂族醇、乙二醇及丙二醇、低聚二醇、这些醇及二醇的醚或酯及其混合物。典型的助溶剂包括:乙二醇、二乙二醇单乙醚、二乙二醇单丁醚及2-丁氧基乙醇。优选的是二乙二醇单丁醚。
涂料组合物可以选择性地包含至少一种烧结粘附组分。典型的使金属涂层与陶瓷基底相结合的烧结粘附组分包括一种或多种金属氧化物,如氧化铜、氧化镉、氧化锌、氧化钡、氧化镁、氧化铝、二氧化硅及一种用钡和铅改性的硼硅酸盐玻璃玻璃料。烧结粘附组分优选地占涂料组合物的约0.1~2%(重量),更优选地在约0.1~0.5%(重量)之间。虽然该涂料组合物主要是用作需后续焙烧的基底上的涂料,但也可以用作将薄银层沉积在不需焙烧的绝缘性或电阻性的材料上,例如陶瓷、石英、铝及塑料或弹性聚合物。当涂料组合物用于涂覆不需焙烧的物体时,可以将组合物中的烧结粘附组分除去,且不会产生不利影响。
涂料组合物通常包含多种不同的添加剂,选自常用的表面活性剂、消泡剂及抗沉降剂。这些添加剂促进了片状银粉在水性载体中的分散。在分散贮存中,银也会发生沉淀。如果在搅拌作用下银不能容易地分散于溶剂中,则组合物就被称为"沉积强烈",而本发明的涂料组合物为弱沉积,即经短时和/或轻微搅拌,固体沉淀物就很容易分散。表面活性剂及消泡剂添加物约占涂料组合物的0.3~6.0%(重量)。优选的表面活性剂及消泡剂添加物的配方包含约占涂料组合物0.1~1.6%(重量),优选占约0.4%(重量)的聚电解质的铵盐分散剂,它购自R.T.Vanderbilt公司,商品名为DarvanC-No.7;还包含约占涂料组合物0.1~0.8%(重量),优选为约0.2%(重量)的2,4,7,9-四甲基-5-癸炔-4,7-二醇消泡型、非离子型表面活性剂,它购自Air Products and Chemicals,Inc.公司,商品名为Surfynol104表面活性剂;还含有约占涂料组合物0.1~0.8%(重量),优选为约0.2%(重量)的改性聚硅氧烷共聚物消泡剂,它购自BYK-ChemieUSA公司,商品名为BYK-020。适用于本发明的抗沉降剂是一种高表面积、分散均匀的无机化合物微粒,如气相法氧化铝、气相法二氧化钛和气相法二氧化硅。粒度约为7~12纳米及比表面积为约200~300米2/克的气相法二氧化硅是优选的。抗沉降剂一般约占涂料组合物的0.1~5.0%(重量),优选占约0.3~1.0%(重量)。
本涂料组合物可用常规设备制备。一般,可充分溶于水的聚合物粘合剂以50%(重量)乳液的形式加入水中,通过加入碱或胺进行中和。能否低于一定的pH值,取决于所用聚合物粘合剂的类型,水性载体的粘度随pH值变化。为了减小粘度受pH影响的敏感度,可加入碱或胺将pH控制在约7~12范围内,优选为约8~10,更优选为约9。作为替换方法,也常使用预中和的聚合物粘合剂,也就是使用溶解于水性介质中的聚合物,再向中和的聚合物粘合剂中加入水和助溶剂,构成水性载体。也可以先用水及助溶剂稀释聚合物粘合剂乳液,再向稀释的乳液中加入碱或胺中和聚合物粘合剂。
重要的一点是,在喷涂之前,聚合物粘合剂是以溶解的状态存在于涂料组合物中。这点与惯用的涂装技术,即成膜助剂激活颜料粘合剂发生在溶剂开始挥发之后有所不同。尽管希望不受特定理论的限制,但认为本发明的涂料组合物大部分具有足够的"未烧结强度",这是因为在溶剂开始挥发之前聚合物粘合剂已经溶解。这里用的"未烧结强度"一词是指银与经低温干燥但未经焙烧的基底表面之间的粘附强度。通常先加入表面活性剂及消泡剂并与液体混合,后加入其余固体组分。优选方法为,先将片状银粉、烧结粘附组分(如需要)和抗沉降剂预混成均匀的组合物,然后再投入水性载体中。可加入少量的水和/或助溶剂将涂料组合物的粘度调节在约0.3~4Pa·s(300~4,000厘泊)之间。当进行这种调节时,可以想到,加入水和助溶剂稀释了片状银粉浓度,降低了通过一次性高速喷涂在基底上得到所需银层厚度的能力。为了喷涂作业,优选的涂料组合物粘度约在0.3~1.6Pa·s(300~1600厘泊)范围内。组分混合时伴随轻微搅拌直至形成均匀分散体。
本涂料组合物还可用喷涂、浸涂或其它惯用方法涂覆于基底,但最适于喷涂。涂覆后,涂料组合物干燥,这使粘合剂成膜,将片状银粉作为金属层与基底粘合。典型的干燥温度可以从环境温度到大约200℃,优选为高于约150℃。干燥过程持续进行,直至几乎完全干燥,通常至少约95%水挥发出去,部分助溶剂也能排出。
本发明的涂料组合物可用于将导电金属层涂覆于其它低导电性或非导电性,即电阻性或绝缘性表面上。尤其适于涂覆电子工业中常用的陶瓷原件。为了使金属层能更牢固地粘结,可再将这些原件在高温下焙烧,一般在温度约600℃~950℃焙烧足够时间,以激活涂料组合物中的烧结粘附组分。继而将原件冷却,烧结粘附组分使金属粘附在陶瓷上。焙烧过程中,聚合物粘合剂及剩余的助溶剂也将挥发和/或热解。本发明涂料组合物的组分是经选择的,因此在焙烧后不会留下显著量的能影响导电金属层电性能的非导电性残余物。
本发明的涂料组合物也可以涂覆于不需焙烧的电阻性或绝缘性的基底上。例如涂覆于塑料或弹性体原件上,之后使这些原件能被电镀。这种应用中,该涂料组合物可被配制成不含烧结粘附组分,并且聚合物粘合剂的量可增加到本发明允许范围的最高点,以提供更大的未烧结强度。
下面用几个有代表性的具体实施例对本发明加以说明,其中所有的份数、比例及百分数均为重量分数,另作说明的除外。所有不符合标准国际单位的重量和尺寸单位已被转化为标准国际单位。涂料组合物的粘度用布氏RVT粘度计测量,用3号测量轴,转速10转/分。
实施例1
将表1所列含量的载体组份混合并搅拌形成水性载体。加入少量单乙醇胺将pH调节为9.5。将载体装入一个3.8升的陶瓷罐中,再加入总体积占陶瓷罐体积50%(体积)的burundum圆柱体,柱体直径为1.25厘米,高为1.25厘米。然后再向罐中加入固体成分,各成分及含量见表1,将罐中成分球磨过夜,则制成涂料组合物。
放置两天后,将组合物于一容器中缓慢转动15分钟,使沉淀的固体物重新分散,测得布氏粘度为1.55Pa·s(1550厘泊),认为它适用于压力进料型喷枪。这种涂料组合物通过加入约2~5%(重量)的水稍加稀释,使粘度降低至约0.5~0.6Pa·s(500~600厘泊),则可适用于虹吸进料型喷枪。
粘度为1.55Pa·s的涂料组合物可以用压力进料型喷枪一次喷涂于钛酸钡或钛酸钕的小陶瓷体上。该湿涂层体在150℃下强制风干10分钟。将低温干燥体在带式炉中焙烧,全部焙烧周期为50分钟,温度分布达峰值875℃时焙烧10分钟。焙烧体上银层厚度为14.8±0.94微米。粘附性的测试方法为:用63锡/37铅焊接剂将一大头针焊接在焙烧体表面上,冷却前焊接剂保持2分钟熔融状态,从焙烧体上拨下大头针所需的力大于20磅。将涂料组合物以一种600平方的蛇形图案涂印在一个氧化铝片上并焙烧,氧化铝片尺寸为0.0625厘米×2.5厘米×5.3厘米,经测试,氧化铝片的电阻率小于2毫欧/平方/25.4微米。
实施例2
用实施例1所述的方法制备表2的涂料组合物。将此组合物设计成为粘度低、喷涂性能良好,并且增加了聚合物粘合剂的量以确保高的未烧结强度。涂料组合物的粘度为1.35Pa·s(1,350厘泊)。用压力进料型喷枪将涂料组合物涂覆于一个小陶瓷体上,然后在150℃风干。将一干净的压敏胶带粘附于已涂覆的表面上,然后再剥离。在胶带上只能看到少量银粉,说明表面涂层有很好的未烧结强度。
实施例3
用实施例1所述方法制备一种浸涂油墨涂料组合物,配方见表3。涂料组合物粘度为2.9Pa·s(2,900厘泊),用人工方法将小陶瓷体缓慢浸入,然后再从油墨浴中取出,就能很容易地被涂覆。被涂体用例1所述方法干燥并焙烧,就形成一层厚度为27.9±3.8微米的涂层,具有与例1相似的粘附性和电阻率。
对比例4-9
按实施例1的方法制备表4所列的涂料组合物。每种组合物包含0.3%(重量)气相法二氧化硅,0.12%(重量)Cu2O,0.24%(重量)CdO和0.33%(重量)硼硅酸铅玻璃玻璃料,然后把每种组合物从研磨罐转移到储存容器中进行目测,结果归纳于表中。
对比例4和5都使用了一种非水溶性丙烯酸类聚合物粘合剂的水性乳液,银分散不良且聚结。此外,对比例4的组合物中混有过量的助溶剂。
对比例6中观察到的分散不良是过量的聚合物粘合剂和助溶剂引起的,大量的空气夹杂是组成中缺少表面活性剂和消泡剂造成的。
对比例7中使用了粒状银粉,涂料组合物的粘度大于约10Pa·s(10,000厘泊),对喷涂来说是过高的。将样品在没有搅拌的情况下短时储存,这引起了固体沉淀,用刮刀用力搅拌也未能使固体重新分散。
对比例8中使用了较大粒径的片状银粉,部分粒径大于20微米,这种涂料组合物未达到喷涂要求。
对比例9中,可确认片状银粉上的润滑油不是一种脂肪酸。银不能充分分散于载体中,无法形成一种耐久的涂料组合物。
表1克 %(重量) 名称 克 %(重量) 名称
载体 固体122.5*2.00 AcrysolI-2426 2190 73.0 片状银粉***546.1 去离子水 9.0 0.30 Aerosil300气相法二氧化硅12.6 0.42 单乙醇胺 3.6 0.12 Cu2O78.0 2.60 二乙二醇单丁醚 7.2 0.24 CdO4.8 0.16 Surfynol104 9.9 0.33 硼硅酸铅玻璃料**4.8 0.16 BYK -02011.1 0.37 DarvanC-No.7*固体含量为49%(重量)的乳液的重量。**软化点为546℃。***不皂化的有酸性涂层的Heraeus Cermalloy片状粉末。
表 2克 %(重量) 名称 克 %(重量) 名称
载体 固体179.4* 3.00 AcrysolI-62 2190 73.0 片状银粉***470.2 去离子水 9.0 0.30 Aerosil300气相法二氧化硅14.0 0.47 单乙醇胺 3.6 0.12 Cu2O90.2 3.0 二乙二醇单丁醚 7.2 0.24 CdO6.1 0.20 Surfynol 104 9.9 0.33 硼硅酸铅玻璃料**6.1 0.20 BYK-02013.9 0.36 DarvanC-No.7*固体含量为49%(重量)的乳液的重量。**软化点为546℃。***不皂化的有酸性涂层的Heraeus Cermalloy片状粉末。
表3克 %(重量) 名称 克 %(重量) 名称
载体 固体75.6* 1.26 AcrysolI-62 2130 71.0 片状银粉****57.5** 0.94 AcrysolI-2426 12.0 0.40 Aerosil300气相法二氧化硅497.2 去离子水 3.6 0.12 Cu2O11.8 0.40 单乙醇胺 7.2 0.24 CdO174.3 5.81 二乙二醇单丁醚 9.9 0.33 硼硅酸铅玻璃料***4.8 0.16 Surfynol1044.8 0.16 BKY-02011.0 0.37 DarvanC-No.7*固含量为50%(重量)的乳液的重量。**固含量为49%(重量)的乳液的重量。***软化点为546℃。****不皂化的有酸性涂层的Heraeus Cermalloy片状粉末。
表4
银 聚合物粘合剂 助溶剂 表面活性剂(7) 结果
%(重量) 型号 %(重量) 型号 %(重量) 型号 %(重量)%(重量)%(重量)对比例4 60 HCF-38(1) 2.3 Rhoplex 13 2-丁氧基 0.16/0.16/0.37 分散不良,
WL-81(5) 乙醇 结块对比例5 65 HCF-38 2.5 Joncryl 3.4 DEGMBE(*) 0.16/0.16/0.37 分散不良,
1535(6) 结块对比例6 60 HCF-38 4.6 Acrysol 10 2-丁氧基 0/0/0 分散不良,
I-2426 乙醇 产生气泡对比例7 61 HCF-3701 Acrysol 5.3 2-丁氧基 0.16/0.16/0.37 粘度过高,沉淀
粒状粉末(2) 2.0 I-2426 乙醇 固体不能重新
分散对比例8 73 Metz#4(3) 2.0 Acrysol 2.6 DEGMBE 0.16/0.16/0.37 湿银层有泡沫I-2425对比例9 73 Metz#10(4) 2.0 Acrysol 2.6 DEGMBE 0.16/0.16/0.37 片状银粉与载
I-2426 体不相容
(1)不皂化的有酸性涂层的Heraeus Cermalloy片状粉末
(2)Heraeus Cermalloy粒状银粉
(3)含饱和脂肪酸润滑油的粗粒片状粉末,表面积0.7~1.1 米2/克,堆积密度2.8~3.2克/厘米3(4)含非脂肪酸润滑油的片状粉末,表面积0.8~1.0米2/克,堆积密度2.3~2.7克/厘米3(5)Rohm及Haas公司的高分子量、低酸值(酸值为49)、固含量为41.5%(重量)的预中和丙烯酸类乳液(6)S.C.Johnson Co.公司的,加入蜡的苯乙烯/丙烯酸类共聚物的预中和乳液(7)Surfynol104/BYK-020/DarvanC-No.7(8)二乙二醇单丁醚
Claims (17)
1.一种涂料组合物,包括
(a)约30~80%(重量)的涂有润滑油的片状银粉,该润滑油包括至少一种直链羧酸或其盐,含6~18个碳原子,
(b)约1.5~4.5%(重量)的可充分溶于水的聚合物粘合剂,
(c)0~约9.5%(重量)的可充分溶于水的助溶剂,及
(d)有效溶剂量的水,
上述百分数是基于涂料组合物的总重量。
2.权利要求1所述的涂料组合物,包括
(a)约30~80%(重量)的涂有润滑油的片状银粉,润滑油包括至少一种直链羧酸或其盐,含6~18个碳原子,
(b)约1.5~4.0%(重量)的可充分溶于水的聚合物粘合剂,
(c)约0.5~8.0%(重量)的可充分溶于水的助溶剂,及
(d)有效溶剂量的水,
上述百分数是基于涂料组合物的总重量。
3.权利要求1或2所述涂料组合物,其中片状银粉含量约为60~75%(重量)。
4.权利要求1至3中任意一项所述涂料组合物,其中片状银粉由长度小于15微米的层状微粒构成。
5.权利要求1至4中任意一项所述涂料组合物,其中聚合物粘合剂是一种水性乳液聚合物,选自丙烯酸类均聚物和丙烯酸类共聚物。
6.权利要求1至5中任意一项所述涂料组合物,其中聚合物粘合剂的平均分子量约为5,000至80,000,酸值不低于60毫克KOH/克聚合物,玻璃化转变温度约为-10℃至80℃。
7.权利要求6所述涂料组合物,其中聚合物粘合剂的平均分子量约为15,000至60,000,玻璃化转变温度约为25℃至60℃。
8.权利要求1至7中任意一项所述涂料组合物,其中助溶剂选自脂族醇、乙二醇和丙二醇、低聚二醇,上述醇和二醇的醚或脂,上述醇、二醇、醚和酯的混合物,所述助溶剂含2-18个碳原子。
9.权利要求8所述涂料组合物,其中助溶剂选自乙二醇、二乙二醇单乙醚、二乙二醇单丁醚、2-丁氧基乙醇和至少两种由上述物质构成的混合物。
10.权利要求1至9中任意一项所述涂料组合物,其中聚合物粘合剂包括一种有效量的中和剂,将聚合物粘合剂中和至pH约为7~12。
11.权利要求10所述涂料组合物,其中聚合物粘合剂中和至pH约为8~10。
12.权利要求10或11所述涂料组合物,其中中和剂选自氢氧化铵、氢氧化钠、氢氧化钾、单乙醇胺、二甲基氨基乙醇和吗啉。
13.权利要求1至12中任意一项所述涂料组合物,还包含约0.1至2.0%(重量)的烧结粘附组分。
14.权利要求13所述涂料组合物,其中烧结粘附组分至少包括下列的一种:氧化铜、氧化镉、氧化锌、氧化钡、氧化镁、氧化铝、二氧化硅、硼硅酸铅玻璃玻璃料及硼硅酸钡玻璃玻璃料。
15.权利要求13或14所述涂料组合物,主要包括
(a)约60至75%(重量)的涂有润滑油的片状银粉,润滑油包括至少一种直链羧酸或其盐,含6~18个碳原子,所述片状银粉由长度小于15微米的层状微粒构成,
(b)约1.5~4.5%(重量)的可充分溶于水的聚合物粘合剂,
(c)0至约9.5%(重量)的可充分溶于水的助溶剂,
(d)约0.3至6.0%(重量)的至少一种表面活性剂和消泡剂添加物,
(e)约0.1至5.0%(重量)的抗沉降剂,
(f)约0.1-2.0%(重量)烧结粘附组分,及
(g)加入余量的水使总重量达100%(重量),其中(c)和(g)的含量成一定比例,使涂料组合物的粘度约为0.3至4.0Pa·s。
16.权利要求15中所述涂料组合物,其中表面活性剂及消泡剂添加物主要包括:
(i)约0.1至1.6%(重量)的聚电解质的铵盐,
(ii)约0.1至0.8%(重量)的2,4,7,9-四甲基-5-癸炔-4,7-二醇,及
(iii)约0.1至0.8%(重量)的聚硅氧烷共聚物消泡剂,
其中抗沉降剂是含量约为0.3至1.0%(重量)的气相法二氧化硅。
17.权利要求1至16任意一项所述涂料组合物的用途,用于在电阻性或绝缘性基底上形成导电层,其中涂料组合物用喷涂法涂覆于基底,并干燥该被涂覆的基底,还可以选择性地进行焙烧。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US335146 | 1994-11-07 | ||
US335,146 | 1994-11-07 | ||
US08/335,146 US5492653A (en) | 1994-11-07 | 1994-11-07 | Aqueous silver composition |
Publications (2)
Publication Number | Publication Date |
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CN1134962A CN1134962A (zh) | 1996-11-06 |
CN1058741C true CN1058741C (zh) | 2000-11-22 |
Family
ID=23310470
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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CN95121553A Expired - Fee Related CN1058741C (zh) | 1994-11-07 | 1995-11-07 | 水性含银组合物 |
Country Status (9)
Country | Link |
---|---|
US (2) | US5492653A (zh) |
EP (1) | EP0713930B1 (zh) |
KR (1) | KR0174305B1 (zh) |
CN (1) | CN1058741C (zh) |
AT (1) | ATE164892T1 (zh) |
DE (1) | DE69502004T2 (zh) |
ES (1) | ES2115306T3 (zh) |
FI (1) | FI114923B (zh) |
HK (1) | HK1001465A1 (zh) |
Families Citing this family (47)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5492653A (en) * | 1994-11-07 | 1996-02-20 | Heraeus Incorporated | Aqueous silver composition |
JPH0912385A (ja) * | 1995-04-28 | 1997-01-14 | Mitsuboshi Belting Ltd | メッキ用表面処理剤およびこれを付着した基材 |
US5756008A (en) * | 1996-08-14 | 1998-05-26 | E. I. Du Pont De Nemours And Company | Water cleanable silver composition |
DE19638629C2 (de) * | 1996-09-20 | 2000-05-31 | Epcos Ag | Verfahren zum Aufbringen einer elektrisch leitfähigen Grundschicht auf einen Keramikkörper |
DE19647044A1 (de) * | 1996-11-14 | 1998-05-20 | Degussa | Paste für Einbrennschichten |
DE19737685C2 (de) * | 1997-08-29 | 1999-08-12 | Sonderhoff Ernst Fa | Abschirmdichtung |
JP3422233B2 (ja) * | 1997-09-26 | 2003-06-30 | 株式会社村田製作所 | バイアホール用導電性ペースト、およびそれを用いた積層セラミック基板の製造方法 |
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DE19815291B4 (de) * | 1998-04-06 | 2006-05-24 | Ferro Gmbh | Beschichtungszusammensetzung zur Herstellung von elektrisch leitfähigen Schichten |
JPH11329073A (ja) * | 1998-05-19 | 1999-11-30 | Murata Mfg Co Ltd | 導電ペースト及びそれを用いたセラミック電子部品 |
US6576336B1 (en) * | 1998-09-11 | 2003-06-10 | Unitech Corporation, Llc | Electrically conductive and electromagnetic radiation absorptive coating compositions and the like |
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KR100339201B1 (ko) * | 2000-04-19 | 2002-05-31 | 안복현 | 도전성 페인트의 제조방법 및 도전성 페인트 조성물 |
US6817088B1 (en) * | 2000-06-16 | 2004-11-16 | Watlow Electric Msg.C | Termination method for thick film resistance heater |
US20050095410A1 (en) * | 2001-03-19 | 2005-05-05 | Mazurkiewicz Paul H. | Board-level conformal EMI shield having an electrically-conductive polymer coating over a thermally-conductive dielectric coating |
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US8178188B2 (en) * | 2001-04-20 | 2012-05-15 | Panasonic Corporation | Base layer for manufacturing an electronic component by an etching process |
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US7316475B2 (en) * | 2004-11-10 | 2008-01-08 | Robert Wilson Cornell | Thermal printing of silver ink |
JP4613362B2 (ja) * | 2005-01-31 | 2011-01-19 | Dowaエレクトロニクス株式会社 | 導電ペースト用金属粉および導電ペースト |
KR20080035562A (ko) * | 2005-06-09 | 2008-04-23 | 인도프코 인코포레이티드 디/비/에이 내쇼날 스타치 앤드 케미칼 캄파니 | 수성의 인쇄 가능한 전기 전도체 |
US7851545B2 (en) * | 2005-07-15 | 2010-12-14 | Chroma Australia Pty Limited | Paint composition |
US20070215883A1 (en) * | 2006-03-20 | 2007-09-20 | Dixon Michael J | Electroluminescent Devices, Subassemblies for use in Making Electroluminescent Devices, and Dielectric Materials, Conductive Inks and Substrates Related Thereto |
US20080010815A1 (en) * | 2006-07-17 | 2008-01-17 | W.E.T. Automotive Group Ag | Heating tape structure |
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JP4294705B2 (ja) * | 2007-05-30 | 2009-07-15 | Dowaエレクトロニクス株式会社 | 有機物質で被覆された銀微粉の製法および銀微粉 |
CN101781496B (zh) * | 2009-01-16 | 2013-10-02 | 比亚迪股份有限公司 | 一种水性银粉涂料组合物 |
US7935278B2 (en) * | 2009-03-05 | 2011-05-03 | Xerox Corporation | Feature forming process using acid-containing composition |
US20110126897A1 (en) * | 2009-05-20 | 2011-06-02 | E. I. Du Pont De Nemours And Company | Composition for extruding fibers |
CN102034877A (zh) * | 2009-09-30 | 2011-04-27 | 比亚迪股份有限公司 | 一种太阳能电池用导电浆料及其制备方法 |
TW201113233A (en) * | 2009-10-06 | 2011-04-16 | Guo Chun Ying | Method of coating noble metal nanoparticle in glassware |
CN102740997B (zh) * | 2009-11-27 | 2016-02-24 | 特线工业株式会社 | 含有微小金属粒子的组合物 |
GB201009847D0 (en) * | 2010-06-11 | 2010-07-21 | Dzp Technologies Ltd | Deposition method, apparatus, printed object and uses |
WO2013091197A1 (en) * | 2011-12-21 | 2013-06-27 | 3M Innovative Properties Company | Resin composition and dielectric layer and capacitor produced therefrom |
CN103177787B (zh) * | 2011-12-26 | 2016-04-27 | 比亚迪股份有限公司 | 一种用于制备导电银浆的导电粉及导电银浆 |
CN103198876B (zh) * | 2012-01-06 | 2015-09-09 | 任天斌 | 水性纳米电子银浆及其制备方法 |
DE102014105483A1 (de) | 2014-04-17 | 2015-10-22 | Heraeus Sensor Technology Gmbh | Sensorelement, Sensormodul, Messanordnung und Abgasrückführsystem mit einem solchen Sensorelement sowie Herstellungsverfahren |
WO2015187179A1 (en) | 2014-06-06 | 2015-12-10 | Hewlett-Packard Development Company, L.P. | Ink composition |
EP3152268B1 (en) * | 2014-06-06 | 2018-02-21 | Hewlett-Packard Development Company, L.P. | Ink composition |
CN106414626B (zh) | 2014-06-06 | 2020-10-23 | 惠普发展公司,有限责任合伙企业 | 墨水组合物 |
CN117238554B (zh) * | 2023-09-06 | 2024-07-16 | 淮安捷泰新能源科技有限公司 | 一种导电银浆及其制备方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH434588A (de) * | 1962-11-15 | 1967-04-30 | Tesla Np | Verfahren zur Herstellung von Silberpulver |
NL300391A (zh) * | 1962-11-15 | |||
US4032350A (en) * | 1973-03-12 | 1977-06-28 | Owens-Illinois, Inc. | Printing paste vehicle, gold dispensing paste and method of using the paste in the manufacture of microelectronic circuitry components |
US4331714A (en) * | 1979-06-29 | 1982-05-25 | E. I. Dupont De Nemours And Company | Process of making flake silver powders with chemisorbed monolayer of dispersant |
US4715989A (en) * | 1986-01-22 | 1987-12-29 | The B.F. Goodrich Company | Coating for EMI shielding |
US4950423A (en) * | 1986-01-22 | 1990-08-21 | The B. F. Goodrich Company | Coating of EMI shielding and method therefor |
US4826631A (en) * | 1986-01-22 | 1989-05-02 | The B. F. Goodrich Company | Coating for EMI shielding and method for making |
US5062891A (en) * | 1987-08-13 | 1991-11-05 | Ceramics Process Systems Corporation | Metallic inks for co-sintering process |
US4906596A (en) * | 1987-11-25 | 1990-03-06 | E. I. Du Pont De Nemours & Co. | Die attach adhesive composition |
US4851051A (en) * | 1988-09-09 | 1989-07-25 | E. I. Du Pont De Nemours And Company | Process for de-ionizing silver particles |
DE69121449T2 (de) * | 1990-04-12 | 1997-02-27 | Matsushita Electric Ind Co Ltd | Leitende Tintenzusammensetzung und Verfahren zum Herstellen eines dickschichtigen Musters |
US5242623A (en) * | 1991-08-13 | 1993-09-07 | E. I. Du Pont De Nemours And Company | Screen-printable thick film paste composition |
US5252632A (en) * | 1992-11-19 | 1993-10-12 | Savin Roland R | Low cost cathodic and conductive coating compositions comprising lightweight hollow glass microspheres and a conductive phase |
US5286415A (en) * | 1992-12-28 | 1994-02-15 | Advanced Products, Inc. | Water-based polymer thick film conductive ink |
US5346651A (en) * | 1993-08-31 | 1994-09-13 | Cerdec Corporation | Silver containing conductive coatings |
US5431718A (en) * | 1994-07-05 | 1995-07-11 | Motorola, Inc. | High adhesion, solderable, metallization materials |
US5492653A (en) * | 1994-11-07 | 1996-02-20 | Heraeus Incorporated | Aqueous silver composition |
US5565143A (en) * | 1995-05-05 | 1996-10-15 | E. I. Du Pont De Nemours And Company | Water-based silver-silver chloride compositions |
-
1994
- 1994-11-07 US US08/335,146 patent/US5492653A/en not_active Expired - Fee Related
-
1995
- 1995-10-17 US US08/544,038 patent/US5658499A/en not_active Expired - Fee Related
- 1995-11-01 KR KR1019950039220A patent/KR0174305B1/ko not_active IP Right Cessation
- 1995-11-02 EP EP95117196A patent/EP0713930B1/en not_active Expired - Lifetime
- 1995-11-02 DE DE69502004T patent/DE69502004T2/de not_active Expired - Fee Related
- 1995-11-02 ES ES95117196T patent/ES2115306T3/es not_active Expired - Lifetime
- 1995-11-02 AT AT95117196T patent/ATE164892T1/de not_active IP Right Cessation
- 1995-11-07 FI FI955353A patent/FI114923B/fi active IP Right Grant
- 1995-11-07 CN CN95121553A patent/CN1058741C/zh not_active Expired - Fee Related
-
1998
- 1998-01-19 HK HK98100441A patent/HK1001465A1/xx not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
EP0713930B1 (en) | 1998-04-08 |
FI955353A (fi) | 1996-05-08 |
ES2115306T3 (es) | 1998-06-16 |
US5658499A (en) | 1997-08-19 |
DE69502004T2 (de) | 1998-09-24 |
DE69502004D1 (de) | 1998-05-14 |
HK1001465A1 (en) | 1998-06-19 |
CN1134962A (zh) | 1996-11-06 |
KR960017803A (ko) | 1996-06-17 |
EP0713930A1 (en) | 1996-05-29 |
KR0174305B1 (ko) | 1999-03-20 |
ATE164892T1 (de) | 1998-04-15 |
FI955353A0 (fi) | 1995-11-07 |
FI114923B (fi) | 2005-01-31 |
US5492653A (en) | 1996-02-20 |
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