JPH0670193B2 - Copper powder for conductive paint and its manufacturing method - Google Patents
Copper powder for conductive paint and its manufacturing methodInfo
- Publication number
- JPH0670193B2 JPH0670193B2 JP63027235A JP2723588A JPH0670193B2 JP H0670193 B2 JPH0670193 B2 JP H0670193B2 JP 63027235 A JP63027235 A JP 63027235A JP 2723588 A JP2723588 A JP 2723588A JP H0670193 B2 JPH0670193 B2 JP H0670193B2
- Authority
- JP
- Japan
- Prior art keywords
- copper powder
- carboxylic acid
- acid ester
- higher carboxylic
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 160
- 239000003973 paint Substances 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 238000000576 coating method Methods 0.000 claims description 97
- 239000011248 coating agent Substances 0.000 claims description 96
- 239000000203 mixture Substances 0.000 claims description 74
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 72
- 229910052726 zirconium Inorganic materials 0.000 claims description 70
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 68
- 229920000642 polymer Polymers 0.000 claims description 65
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 56
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 239000008199 coating composition Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002612 dispersion medium Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000012799 electrically-conductive coating Substances 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- -1 solder Chemical compound 0.000 description 13
- 230000000694 effects Effects 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 241001311547 Patina Species 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000007650 screen-printing Methods 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 235000020778 linoleic acid Nutrition 0.000 description 5
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 4
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 229920000297 Rayon Polymers 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000000113 methacrylic resin Substances 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 235000021313 oleic acid Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- GLYJVQDYLFAUFC-UHFFFAOYSA-N butyl hexadecanoate Chemical compound CCCCCCCCCCCCCCCC(=O)OCCCC GLYJVQDYLFAUFC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 2
- OCAIYHCKLADPEG-UHFFFAOYSA-N propan-2-yl pentanoate Chemical compound CCCCC(=O)OC(C)C OCAIYHCKLADPEG-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000004671 saturated fatty acids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- AMEMLELAMQEAIA-UHFFFAOYSA-N 6-(tert-butyl)thieno[3,2-d]pyrimidin-4(3H)-one Chemical compound N1C=NC(=O)C2=C1C=C(C(C)(C)C)S2 AMEMLELAMQEAIA-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- UTDKTXORJIVKDX-UHFFFAOYSA-N CC(C)(C)O[Zr] Chemical compound CC(C)(C)O[Zr] UTDKTXORJIVKDX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- RPRPDTXKGSIXMD-UHFFFAOYSA-N butyl hexanoate Chemical compound CCCCCC(=O)OCCCC RPRPDTXKGSIXMD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 125000003450 decanoic acid ester group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229940024423 isopropyl isobutyrate Drugs 0.000 description 1
- 229940093629 isopropyl isostearate Drugs 0.000 description 1
- 229940033357 isopropyl laurate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940049918 linoleate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- XEIOPEQGDSYOIH-MURFETPASA-N propan-2-yl (9z,12z)-octadeca-9,12-dienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OC(C)C XEIOPEQGDSYOIH-MURFETPASA-N 0.000 description 1
- NEOZOXKVMDBOSG-UHFFFAOYSA-N propan-2-yl 16-methylheptadecanoate Chemical compound CC(C)CCCCCCCCCCCCCCC(=O)OC(C)C NEOZOXKVMDBOSG-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- IZUZIVIUDTZPFE-UHFFFAOYSA-N tert-butyl decanoate Chemical compound CCCCCCCCCC(=O)OC(C)(C)C IZUZIVIUDTZPFE-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は導電塗料用銅粉に関し、より詳細には、銅粉
の導電性と電磁波遮蔽（シールド）効果を低下させるこ
となく、銅粉自体および導電塗料の貯蔵安定性および耐
環境性、並びに塗膜の密着性を向上させた導電塗料用銅
粉およびその製造法、並びに導電性塗料組成物に関す
る。Description: TECHNICAL FIELD The present invention relates to a copper powder for a conductive coating, and more specifically, to the copper powder itself without lowering the conductivity and electromagnetic wave shielding effect of the copper powder. The present invention also relates to a copper powder for a conductive coating, which has improved storage stability and environment resistance of the conductive coating, and adhesion of a coating film, a method for producing the same, and a conductive coating composition.
［従来の技術］ 電子機器を電磁波の妨害から保護する電磁波シールド材
料の一つとして、従来、ニッケル粉、銀粉、銅粉、カー
ボン粉などの導電性フィラーを各種の結合剤樹脂に混練
した導電性塗料があり、この塗料をプラスチックス成形
品表面にスプレー、ハケなどで塗布して電磁波をシール
ドする。各種の導電性塗料のうち銅系導電性塗料は、銀
粉やニッケル粉を用いる塗料より廉価であり、シールド
効果に優れた特性を有する。[Prior Art] As one of electromagnetic wave shield materials for protecting electronic devices from electromagnetic interference, conventionally, conductive fillers such as nickel powder, silver powder, copper powder, carbon powder and the like are kneaded with various binder resins. There is paint, and this paint is applied to the surface of the plastic molded product by spraying or brushing to shield electromagnetic waves. Among various conductive paints, the copper-based conductive paint is cheaper than the paint using silver powder or nickel powder, and has excellent shielding effect.
しかしながら、銅系導電性塗料は、塗料中で銅粉が凝集
して良好な分散状態が得られず貯蔵安定性に劣り、しか
も、熱、湿度などの環境で酸化されやすく、従って、耐
環境性および導電性の劣化（シールド効果の減衰）を起
しやすいという問題点がある。この問題点を解消するた
めに従来種々の提案がなされている。例えば、銅粉に結
合剤樹脂および有機チタネートを配合して導電塗料を製
造すること（特開昭56−36553号公報）、銅粉をカップ
リング剤で表面処理すること（特開昭60−30200号公
報）、電解銅粉を有機チタネートで被覆すること（特開
昭59−174661号公報）、銅粉を有機アルミニウムで被覆
すること（特開昭59−179671号公報）などが提案されて
いる他、種々の提案がある（特開昭60−258273号公報、
特開昭60−243277号公報、特開昭60−35405号公報、特
開昭57−113505号公報、特開昭60−63239号公報、特開
昭61−163975号公報、特開昭58−145769号公報、特開昭
60−202166号公報、特開昭56−103260号公報、特開昭58
−74759号公報、特開昭56−163166号公報、特開昭56−1
63165号公報、特開昭59−36170号公報、特開昭57−3460
6号公報）。However, the copper-based conductive paint is inferior in storage stability because copper powder is agglomerated in the paint and a good dispersion state cannot be obtained, and moreover, it is easily oxidized in an environment such as heat and humidity, and therefore, it has environmental resistance. Also, there is a problem that conductivity is easily deteriorated (shielding effect is attenuated). Various proposals have heretofore been made to solve this problem. For example, a conductive coating is prepared by mixing a binder resin and an organic titanate with copper powder (JP-A-56-36553), and surface treatment of copper powder with a coupling agent (JP-A-60-30200). Japanese Patent Laid-Open Publication No. 59-179671), coating electrolytic copper powder with organic titanate (JP-A-59-174661), coating copper powder with organic aluminum (JP-A-59-179671), and the like. In addition, there are various proposals (JP-A-60-258273,
JP-A-60-243277, JP-A-60-35405, JP-A-57-113505, JP-A-60-63239, JP-A-61-163975, JP-A-58- 145769, JP Sho
60-202166, JP-A-56-103260, JP-A-58
-74759, JP-A-56-163166, JP-A-56-1
63165, JP 59-36170, JP 57-3460
No. 6).
これらの銅粉から得られた導電性塗料は、銅粉の導電性
と電磁波シールド効果を低下させることなく、ある程
度、貯蔵安定性および耐環境性を向上させることができ
る。The conductive paint obtained from these copper powders can improve storage stability and environmental resistance to some extent, without reducing the conductivity and electromagnetic wave shielding effect of copper powder.
［発明が解決しようとする課題］ しかしながら、従来の銅粉から得られた導電性塗料は、
基材に塗布して使用した場合、基材に対する密着性が劣
り、また、銅粉自体および塗料が必ずしも優れた貯蔵安
定性および耐環境性を示していない。[Problems to be Solved by the Invention] However, the conductive paint obtained from the conventional copper powder is
When used by coating on a substrate, the adhesion to the substrate is inferior, and the copper powder itself and the coating do not always show excellent storage stability and environmental resistance.
この発明は上述の背景に基づきなされたものであり、そ
の目的とするところは、上記の従来の導電塗料用銅粉お
よび導電性塗料の欠点を解消して、銅粉の導電性と電磁
波シールド効果を低下させることなく、銅粉自体および
塗料の貯蔵安定性および耐環境性、並びに塗膜の密着性
を向上させた導電塗料用銅粉およびその製造法、並びに
導電性塗料組成物を提供することである。This invention has been made based on the above background, and its purpose is to eliminate the drawbacks of the above-mentioned conventional copper powder for conductive paint and conductive paint, the conductivity of the copper powder and the electromagnetic wave shielding effect. To provide a copper powder for a conductive coating, which has improved storage stability and environment resistance of the copper powder itself and coating material, and adhesion of a coating film, and a method for producing the same, and a conductive coating composition without decreasing the temperature. Is.
本発明者は導電塗料用銅粉について種々の試験研究を行
った結果、ジルコニウムアシレートポリマーと高級カル
ボン酸との混合物を銅粉表面に被覆させることにより、
基材に対する優れた塗料の密着性を示すとの知見を得、
この発明を完成するに至った。The present inventor has conducted various test studies on copper powder for conductive paints, by coating the surface of the copper powder with a mixture of a zirconium acylate polymer and a higher carboxylic acid,
We obtained the knowledge that it shows excellent adhesion of the coating material to the base material,
The present invention has been completed.
すなわち、この発明の導電塗料用銅粉は、銅粉の表面
に、ジルコニウムアシレートポリマーおよび高級カルボ
ン酸エステルが被覆されたことを特徴とするものであ
る。That is, the copper powder for conductive paint of the present invention is characterized in that the surface of the copper powder is coated with a zirconium acylate polymer and a higher carboxylic acid ester.
この発明の好ましい態様において、ジルコニウムアシレ
ートポリマーと高級カルボン酸エステルとの混合比は、
ジルコニウムアシレートポリマー10〜90重量％に対して
高級カルボン酸エステル90〜10重量％である。In a preferred embodiment of the present invention, the mixing ratio of zirconium acylate polymer and higher carboxylic acid ester is
The content of the higher carboxylic acid ester is 90 to 10% by weight based on 10 to 90% by weight of the zirconium acylate polymer.
この発明による導電性塗料用銅粉の製造法は、銅粉の分
散浴に、ジルコニウムアシレートポリマーと高級カルボ
ン酸エステルとの混合物を添加して銅粉の表面にジルコ
ニウムアシレートポリマーおよび高級カルボン酸エステ
ルの被膜を形成し、必要に応じて、分散媒を除去し、導
電塗料用銅粉を得ることを特徴とするものである。The method for producing a copper powder for a conductive coating according to the present invention comprises adding a mixture of a zirconium acylate polymer and a higher carboxylic acid ester to a copper powder dispersion bath to form a zirconium acylate polymer and a higher carboxylic acid on the surface of the copper powder. It is characterized in that a film of ester is formed and, if necessary, the dispersion medium is removed to obtain copper powder for conductive paint.
この発明による導電塗料組成物は、第一の態様で、ジル
コニウムアシレートポリマーおよび高級カルボン酸エス
テルが被覆された被覆銅粉と、結合剤樹脂と、溶剤とを
含むものであり、第二の態様で、ジルコニウムアシレー
トポリマーおよび高級カルボン酸エステルとの混合物
が、銅粉、結合剤樹脂および溶剤の混合系に、添加され
たものである。A conductive coating composition according to the present invention is, in the first aspect, a coating copper powder coated with a zirconium acylate polymer and a higher carboxylic acid ester, a binder resin, and a solvent, and a second aspect. Then, the mixture of the zirconium acylate polymer and the higher carboxylic acid ester is added to the mixed system of the copper powder, the binder resin and the solvent.
以下、この発明をより詳細に説明する。Hereinafter, the present invention will be described in more detail.
銅粉 この発明で用いられる銅粉の形状は、電解法、還元法、
アトマイズ法より得られる樹枝状、粒状、球状があり、
更に、これらをボールミルなどで機械的に加工したフレ
ーク状などがある。Copper powder The shape of the copper powder used in the present invention is electrolysis, reduction,
There are dendritic, granular and spherical shapes obtained by the atomizing method,
Further, there are flakes formed by mechanically processing these with a ball mill or the like.
また、Ｖ型ミキサーなどを用いて樹枝状銅粉、フレーク
状銅粉、粒状銅粉、および球状銅粉を混合して用いるこ
とができる。Further, a dendritic copper powder, flaky copper powder, granular copper powder, and spherical copper powder can be mixed and used by using a V-type mixer or the like.
さらに、この発明において用いることができる原料の銅
粉として、銀、ニッケル、亜鉛、白金、パラジウムなど
の金属、半田などの合金、有機ケイ素化合物、有機チタ
ン化合物や有機アルミニウム化合物などの金属有機化合
物、界面活性剤、アミノ酸、カルボン酸およびその誘導
体などで予め被覆していてもよい。好ましい原料の被覆
銅粉として、銀被覆銅粉がある。銀被覆量は銅成分に対
して0.1〜20重量％、好ましくは1.0〜10重量％である。
これは上記の下限値未満では耐酸化性に劣り、上限値を
超えると製造コストが高くなるからである。この銀被覆
銅粉を用いることによって、未被覆銅粉よりもシールド
効果に優れた塗膜を得ることができ，結合剤樹脂として
フェノール、エポキシ樹脂などの熱硬化性樹脂の適用も
できる。この銀被覆法としては化学置換メッキ法、CVD
法、機械的結合法などがある。Further, as the raw material copper powder that can be used in the present invention, silver, nickel, zinc, platinum, metals such as palladium, alloys such as solder, organic silicon compounds, metal organic compounds such as organic titanium compounds and organic aluminum compounds, It may be previously coated with a surfactant, an amino acid, a carboxylic acid and its derivative. A preferred raw material coated copper powder is silver-coated copper powder. The silver coating amount is 0.1 to 20% by weight, preferably 1.0 to 10% by weight, based on the copper component.
This is because if it is less than the above lower limit, the oxidation resistance is inferior, and if it exceeds the upper limit, the manufacturing cost increases. By using this silver-coated copper powder, a coating film having a better shielding effect than uncoated copper powder can be obtained, and a thermosetting resin such as phenol or epoxy resin can be applied as the binder resin. As this silver coating method, chemical displacement plating method, CVD
Law, mechanical coupling method, etc.
処理すべき銅粉は、前処理として必要に応じて、無機
酸、有機産、各種還元剤などの試薬を用いたり、または
アンモニア、水素などの還元性ガスにより、銅粉表面か
らの酸化被覆を除去されることができる。また、処理す
べき銅粉を、前処理として乾燥することができる。As a pretreatment, the copper powder to be treated may be treated with a reagent such as an inorganic acid, an organic substance, various reducing agents, or an oxidizing coating from the surface of the copper powder with a reducing gas such as ammonia or hydrogen. Can be removed. Further, the copper powder to be treated can be dried as a pretreatment.
ジルコニウムアシレートポリマー 銅粉に被覆される成分の一つが、ジルコニウムアシレー
トポリマーである。Zirconium Acylate Polymer One of the components coated with copper powder is a zirconium acylate polymer.
この発明において用いられるジルコニウムアシレートポ
リマーは、下記繰返し単位Ｉ、IIおよび／またはIIIを
有する。The zirconium acylate polymer used in the present invention has the following repeating units I, II and / or III.
（式中、Ｒ、R1、R2およびR3は、同種または異種の炭素
数１〜25、好ましくはＲは炭素数１〜10の炭化水素基、
R1、R2およびR3は、８〜24の炭化水素基である） この発明において用いられるジルコニウムアシレートポ
リマーは、前記の他、次の様にも特定され、これらのい
ずれかの定義に当て嵌まるものである。 (In the formula, R, R 1 , R 2 and R 3 are the same or different and have 1 to 25 carbon atoms, preferably R is a hydrocarbon group having 1 to 10 carbon atoms,
R 1 , R 2 and R 3 are hydrocarbon groups of 8 to 24) The zirconium acylate polymer used in the present invention is specified as follows in addition to the above, and is defined in any of these definitions. That is the case.
すなわち、ジルコニウムアシレートポリマーは，主鎖
（−Zr−Ｏ）ｎのジルコニウム原子に結合した易加水分
解性アルコキシ基と、同じくジルコニウム原子に結合し
た難加水分解性かつ親油性のアシレート基とを有するも
のであり、または、 ジルコニウムアシレートポリマーが下記一般式Ａ、Ｂま
たは／およびＣで表されるものである。That is, the zirconium acylate polymer has an easily hydrolyzable alkoxy group bonded to the zirconium atom of the main chain (-Zr-O) n and a hardly hydrolyzable and lipophilic acylate group also bonded to the zirconium atom. Or the zirconium acylate polymer is represented by the following general formula A, B or / and C.
（式中、ROは加水分解され易いアルコキシ基であり、OC
OR′は加水分解され難くかつ親油性を示すアシレート基
であり、Ｒ″は水素原子、ＲまたはCOR′であり、ｎは
ｎ≧１を満足する） このジルコニウムアシレートポリマーは、テトラアルコ
キシジルコニウムZr（OR）４にカルボン酸、酸無水物、
無機酸などを作用させて、またテトラクロロジルコニウ
ムZr（Cl）４にアンモニア／カルボン酸、カルボン酸ナ
トリウム塩などを作用させて得ることができる。 (In the formula, RO is an alkoxy group which is easily hydrolyzed, and
OR 'is a hydrolyzable and lipophilic acylate group, R "is a hydrogen atom, R or COR', and n satisfies n≥1.) This zirconium acylate polymer is tetraalkoxyzirconium Zr. (OR) 4 , carboxylic acid, acid anhydride,
It can be obtained by acting an inorganic acid or the like, or by acting ammonia / carboxylic acid, sodium carboxylic acid salt or the like on tetrachlorozirconium Zr (Cl) 4 .
好ましいジルコニウムアシレートポリマーの合成法は、
テトラアルコキシジルコニウムZr（OR）４に数倍モルの
カルボン酸、特に高級脂肪酸を作用する方法である。こ
れは、次のような理由による。第一に、モノアシレート
化合物やジルコニウムアルコキンポリマーの生成を押さ
え、ジルコニウムアシレートポリマーを定量的に得るこ
とができ、第二に、反応副生物として塩化物や無機酸な
どを生じず、第三に、高級脂肪酸を用いることで、ジル
コニウムアシレートポリマーの側鎖が高級脂肪酸により
アシル化されてジルコニウムアシレートポリマー膜をよ
り疎水性にし、さらに、得られた反応混合物をこの発明
の銅粉の製造における試薬として用いることができるか
らである。A preferred method for synthesizing zirconium acylate polymer is
It is a method in which tetra-alkoxyzirconium Zr (OR) 4 is reacted with several times mole of carboxylic acid, especially higher fatty acid. This is for the following reason. First, it is possible to quantitatively obtain a zirconium acylate polymer by suppressing the production of a monoacylate compound or zirconium alcoquine polymer. Secondly, chloride or inorganic acid is not generated as a reaction by-product, and thirdly, By using a higher fatty acid, the side chain of the zirconium acylate polymer is acylated by the higher fatty acid to make the zirconium acylate polymer film more hydrophobic, and further the obtained reaction mixture is used in the production of the copper powder of the present invention. This is because it can be used as a reagent.
テトラアルコキシジルコニウムZr（OR）４に数倍モルの
カルボン酸またはそれらの異性体から調製する方法は、
例えば、テトライソプロポキシジルコニウム、テトラｔ
−ブトキシジルコニウム、テトラｎ−ブトキシジルコニ
ウム、テトライソブトキシジルコニウム１モルに対し
て、１モル以上の、好ましくは３〜６モルのステアリン
酸、パルミチン酸、ミスチリン酸、ラウリル酸、カプリ
ン酸などの高級飽和脂肪酸およびその異性体、オレイン
酸、リノール酸、リノレイン酸などの高級不飽和脂肪酸
およびその異性体を作用させることからなる。A method for preparing tetraalkoxyzirconium Zr (OR) 4 from several times the moles of carboxylic acid or their isomers is
For example, tetraisopropoxy zirconium, tetra t
-Butoxy zirconium, tetra n-butoxy zirconium, tetraisobutoxy zirconium 1 mol or more, preferably 3 to 6 mol of higher saturated stearic acid, palmitic acid, mistyric acid, lauric acid, capric acid, etc. It comprises reacting a fatty acid and its isomer, a higher unsaturated fatty acid such as oleic acid, linoleic acid and linoleic acid, and its isomer.
合成されたジルコニウムアシレートポリマーの分離精製
は、蒸溜、抽出、再結晶、カラムクロマトグラフィーな
どの手法で行うことができる。Separation and purification of the synthesized zirconium acylate polymer can be carried out by techniques such as distillation, extraction, recrystallization and column chromatography.
高級カルボン酸エステル この発明での高級カルボン酸エステルは、長鎖の多数の
炭素を有するものであり、好ましいそのエステルとし
て、高級脂肪酸アシレート基と、易加水分解性アルコキ
シ基とからなるものがある。Higher Carboxylic Acid Ester The higher carboxylic acid ester of the present invention has a large number of long-chain carbon atoms, and preferred esters thereof include those having a higher fatty acid acylate group and an easily hydrolyzable alkoxy group.
この発明において用いることができる高級カルボン酸エ
ステルは、また次のように定義できる。The higher carboxylic acid ester that can be used in the present invention can be defined as follows.
（式中、ＲCOOは飽和または不飽和の脂肪酸アシレー
ト基を、Ｒ′Ｏは加水分解され易いアルコキシ基を表
す） このエステルの高級カルボン酸に対応する部分は、炭素
数８〜24の高級脂肪酸アシレート基であり、このエステ
ルのアルコールに対応する部分は、炭素数１〜15、好ま
しくは炭素数１〜10のアルコキシ基である。 (In the formula, RCOO represents a saturated or unsaturated fatty acid acylate group, and R'O represents an easily hydrolyzed alkoxy group.) The portion of this ester corresponding to the higher carboxylic acid is a higher fatty acid acylate having 8 to 24 carbon atoms. The part of the ester corresponding to the alcohol is an alkoxy group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
このような高級カルボン酸エステルの具体例には、ステ
アリン酸エステル、パルミチン酸エステル、ミスチリン
酸エステル、ラウリン酸エステル、カプリン酸エステル
などの高級飽和脂肪酸およびこれらの異性体、オレイン
酸エステル、リノール酸エステル、リノレイン酸エステ
ルなどの高級不飽和脂肪酸およびこれらの異性体などが
ある。これは、用いるカルボン酸エステルが低級である
と銅粉表面に形成されたカルボン酸エステル膜の疎水性
が損なわれると共に、結合剤樹脂との塗料および塗膜形
成において、銅粉の良好な分散状態が得られないからで
ある。Specific examples of such higher carboxylic acid ester include higher saturated fatty acids such as stearic acid ester, palmitic acid ester, mistyric acid ester, lauric acid ester, and capric acid ester, and their isomers, oleic acid ester, and linoleic acid ester. , Higher unsaturated fatty acids such as linoleic acid ester and isomers thereof. This is because when the carboxylic acid ester used is low, the hydrophobicity of the carboxylic acid ester film formed on the surface of the copper powder is impaired, and a good dispersion state of the copper powder is obtained in the formation of paints and coating films with the binder resin. Because I can't get it.
この発明において用いることができる高級カルボン酸エ
ステルは、一般的に高級カルボン酸にアルコールを作用
させて得ることができる他、ジルコニウムアシレートポ
リマーを合成する際に副生するエステルを用いることが
できる。The higher carboxylic acid ester that can be used in the present invention can be generally obtained by reacting a higher carboxylic acid with an alcohol, or an ester that is by-produced when synthesizing a zirconium acylate polymer can be used.
ジルコニウムアシレートポリマーと高級コルボン酸エス
テルとの混合物を、テトラアルコキシジルコニウムと高
級カルボン酸との反応混合物から得る場合、テトラアル
コキシジルコニウム１モルと高級カルボン酸２〜８モ
ル、好ましくはテトラアルコキシジルコニウム１モルと
高級カルボン酸３〜６モルとの割合で得ることが好まし
い。これはこの範囲より少ないと、単なるアシレート、
例えばモノアシレート、ジルコニウムアルコキシポリマ
ーが生成してジルコニウムアシレートポリマーが生成せ
ず、この範囲より多くなるとジルコニウムアシレートポ
リマーが定量的に得られるが副生成物であるカルボン酸
エステルやアルコールが過剰に増加するからである。こ
こで用いるテトラアルコキシジルコニウムのアルコキシ
基の炭素数は、１〜15、好ましくは１〜10である。これ
は炭素数が10を超えると銅粉表面吸着水との加水分解反
応が速やかに進行しなくなったり、カルボン酸とのアシ
レート形成の反応性が低下し、また15を超えるとその反
応性が著しく低下し殆ど反応が進行しなくなるからであ
る。When a mixture of zirconium acylate polymer and higher carboxylic acid ester is obtained from a reaction mixture of tetraalkoxyzirconium and higher carboxylic acid, 1 mol of tetraalkoxyzirconium and 2 to 8 mol of higher carboxylic acid, preferably 1 mol of tetraalkoxyzirconium. Is preferably obtained in a ratio of 3 to 6 mol of higher carboxylic acid. If this is less than this range, mere acylate,
For example, a monoacylate or zirconium alkoxy polymer is produced and a zirconium acylate polymer is not produced. When the amount exceeds this range, a zirconium acylate polymer is quantitatively obtained, but by-products such as carboxylic acid ester and alcohol increase excessively. Because. The number of carbon atoms of the alkoxy group of the tetraalkoxyzirconium used here is 1 to 15, preferably 1 to 10. This is because when the carbon number exceeds 10, the hydrolysis reaction with the copper powder surface adsorbed water does not proceed promptly, the reactivity of the acylate formation with the carboxylic acid decreases, and when it exceeds 15, the reactivity is remarkably increased. This is because the reaction temperature decreases and the reaction hardly progresses.
合成されたカルボン酸エステルの分離精製は、蒸溜、抽
出、再結晶、カラムクロマトグラフィーなどの手法で行
うことができる。Separation and purification of the synthesized carboxylic acid ester can be carried out by techniques such as distillation, extraction, recrystallization and column chromatography.
導電塗料用銅粉の製造法 この発明による製造法は、銅粉の分散浴に、ジルコニウ
ムアシレートポリマーと高級カルボン酸エステルとの混
合物を添加して銅粉の表面にジルコニウムアシレートポ
リマーおよび高級カルボン酸エステルの被膜を形成し、
必要に応じて分散媒を除去し、導電塗料用銅粉を得るこ
とを含むものである。Manufacturing Method of Copper Powder for Conductive Coating In the manufacturing method according to the present invention, a mixture of a zirconium acylate polymer and a higher carboxylic acid ester is added to a dispersion bath of copper powder to form a zirconium acylate polymer and a higher carboxyl group on the surface of the copper powder. Form a film of acid ester,
If necessary, the dispersion medium is removed to obtain copper powder for conductive paint.
この製造法における銅粉の分散浴は、被覆すべき銅粉が
分散媒によって良好に分散状態を形成しているものであ
り、ここで用いられる分散媒として、例えば、水、アル
コールなどの有機溶媒がある。好ましい分散媒として、
水、メチルアルコール、エチルアルコール、トルエン、
ヘキサンなどがある。この分散媒の量は、銅粉の分散状
態を良好に形成するに必要な量であり、できるだけ最少
量に設定することが好ましい。これは、分散媒の量が多
くなると、ジルコニウムアシレートポリマーと高級カル
ボン酸エステルとの混合物と銅粉の表面との反応速度が
低下し、所望の銅粉を得ることが難しくなるからであ
る。The dispersion bath of copper powder in this production method is one in which the copper powder to be coated forms a good dispersed state by the dispersion medium. As the dispersion medium used here, for example, water, an organic solvent such as alcohol, or the like. There is. As a preferred dispersion medium,
Water, methyl alcohol, ethyl alcohol, toluene,
Hexane, etc. The amount of this dispersion medium is an amount necessary to form a good dispersion state of the copper powder, and it is preferable to set it to the minimum amount possible. This is because when the amount of the dispersion medium increases, the reaction rate between the mixture of the zirconium acylate polymer and the higher carboxylic acid ester and the surface of the copper powder decreases, making it difficult to obtain the desired copper powder.
添加されるジムコニウムアシレートポリマーと高級カル
ボン酸エステルとの混合物は、ジルコニウムアシレート
ポリマーおよび高級カルボン酸エステルを各々所定量ず
つ混合して得ることができると共に、前述のようにテト
ラアルコキシジルコニウムと高級カルボン酸との反応混
合物から得ることができる。The mixture of the added zimconium acylate polymer and the higher carboxylic acid ester can be obtained by mixing the zirconium acylate polymer and the higher carboxylic acid ester in predetermined amounts, and as described above, the tetraalkoxy zirconium and the higher carboxylic acid ester can be mixed. It can be obtained from a reaction mixture with a carboxylic acid.
この混合物のジルコニウムアシレートポリマーと高級カ
ルボン酸エステルとの混合比は、ジルコニウムアシレー
トポリマー５〜95重量％に対して高級カルボン酸エステ
ル95〜５重量％、好ましくはジルコニウムアシレートポ
リマー10〜90重量％に対して高級カルボン酸エステル90
〜10重量％、より好ましくはジルコニウムアシレートポ
リマー20〜80重量％に対して高級カルボン酸エステル80
〜20重量％である。これは、ジルコニウムアシレートポ
リマーがこの範囲の下限未満だと、疎水性が著しく劣
り、ジルコニウムアシレートポリマーがこの範囲の上限
を超えると導電性が徐々に低下するからである。また、
高級カルボン酸エステルが、この範囲の下限未満だと、
塗料および塗膜形成における銅粉の分散性が著しく劣
る。The mixing ratio of the zirconium acylate polymer and the higher carboxylic acid ester in this mixture is 95 to 5% by weight, preferably 10 to 90% by weight of the higher carboxylic acid ester, based on 5 to 95% by weight of the zirconium acylate polymer. 90% higher carboxylic ester
-10% by weight, more preferably 20-80% by weight of zirconium acylate polymer, and 80 higher carboxylic acid ester.
~ 20% by weight. This is because if the zirconium acylate polymer is less than the lower limit of this range, the hydrophobicity is remarkably inferior, and if the zirconium acylate polymer exceeds the upper limit of this range, the conductivity gradually decreases. Also,
If the higher carboxylic acid ester is below the lower limit of this range,
The dispersibility of copper powder in paint and film formation is extremely poor.
ジルコニウムアシレートポリマーと高級カルボン酸エス
テルとの混合物を、例えば、有機溶媒で希釈することが
できる。ここで用いることができる有機溶媒として、好
ましくはトルエンやヘキサンなどの非極性溶媒の他、ア
ルコールやアセトンなどの極性溶媒がある。The mixture of zirconium acylate polymer and higher carboxylic acid ester can be diluted with, for example, an organic solvent. The organic solvent that can be used here is preferably a non-polar solvent such as toluene or hexane, or a polar solvent such as alcohol or acetone.
銅粉に対するジルコニウムアシレートポリマーと高級カ
ルボン酸エステルとの混合物の処理量は、0.05〜15重量
％、好ましくは0.1〜10重量％である。これは、0.05重
量％未満では銅粉表面の改質が不十分であり、塗料の導
電性、耐環境性および塗膜の化学的、物理的強度が低下
し始め、0.01重量％未満ではその傾向が著しくなる。他
方10重量％を超えると銅粉表面に過剰の塗膜が形成され
て塗料の導電性、耐環境性および塗膜の化学的物理的強
度が低下し始め、15重量％を超えるとその傾向が著しく
なる。The treatment amount of the mixture of zirconium acylate polymer and higher carboxylic acid ester with respect to the copper powder is 0.05 to 15% by weight, preferably 0.1 to 10% by weight. This is because if the content is less than 0.05% by weight, the modification of the surface of the copper powder is insufficient, and the electrical conductivity, environmental resistance of the paint and the chemical and physical strength of the coating film begin to decline, and if less than 0.01% by weight, the tendency tends to decrease. Becomes noticeable. On the other hand, if it exceeds 10% by weight, an excessive coating film is formed on the surface of the copper powder, and the electrical conductivity, environment resistance of the coating material and the chemical and physical strength of the coating film start to decline, and if it exceeds 15% by weight, this tendency tends to occur. It will be noticeable.
銅粉の分散浴へのジルコニウムアシレートポリマーと高
級カルボン酸エステルとの混合物の添加は、例えば、少
量ずつ直接にその分散浴に添加するか、また有機溶媒、
水などで希釈して添加する。添加速度、添加後の攪拌時
間などの操作パラメータは、銅粉の表面状態、すなわち
吸着水量、比表面積、形状などに応じて適宜選択するこ
とが望ましい。Addition of a mixture of a zirconium acylate polymer and a higher carboxylic acid ester to a dispersion bath of copper powder may be carried out, for example, by directly adding a small amount to the dispersion bath, or by adding an organic solvent,
Dilute with water etc. and add. Operation parameters such as addition rate and stirring time after addition are preferably selected appropriately according to the surface state of the copper powder, that is, the amount of adsorbed water, the specific surface area, the shape and the like.
ジルコニウムアシレートポリマーおよび高級カルボン酸
エステルの被膜を形成した後、必要に応じて、分散媒を
除去する。これは、場合により、乾燥が不十分であれ
ば、銅粉の酸化が起って良好な導電性やシールド効果を
得ることができず、変色や緑青が発生する恐れがあるか
らである。After forming the film of the zirconium acylate polymer and the higher carboxylic acid ester, the dispersion medium is removed if necessary. This is because in some cases, if the drying is insufficient, oxidation of the copper powder may occur, and good conductivity and shielding effect may not be obtained, and discoloration or patina may occur.
導電性塗料組成物 得られたこの発明の銅粉は、結合剤樹脂および溶剤など
と混合されて、導電性塗料組成物として用いることがで
きる。Conductive Coating Composition The obtained copper powder of the present invention can be mixed with a binder resin, a solvent and the like to be used as a conductive coating composition.
また、ジルコニウムアシレートポリマーおよび高級カル
ボン酸エステルとの混合物を、銅粉、結合剤樹脂および
溶剤の混合系に、添加しても導電性塗料組成物として用
いることができる。Further, even if a mixture of the zirconium acylate polymer and the higher carboxylic acid ester is added to the mixed system of the copper powder, the binder resin and the solvent, it can be used as a conductive coating composition.
この発明において用いることのできる結合剤樹脂には、
通常に電子機器によく用いられているプラスチックスに
対して密着性良好な熱可塑性樹脂および熱硬化性樹脂が
ある。例えば、アクリル、ABS、ポリスチレン、PPO、ポ
リカーボネートなどの電子機器筐体用プラスチックスに
対し、アクリル系樹脂、ポリウレタン系樹脂、ポリエス
テル系樹脂、スチレン系樹脂、フェノール系樹脂、エポ
キシ系樹脂などを用いることができる。Binder resins that can be used in this invention include
There are thermoplastic resins and thermosetting resins that have good adhesion to plastics that are commonly used in electronic devices. For example, acrylic resin, polyurethane resin, polyester resin, styrene resin, phenol resin, epoxy resin, etc. should be used for plastics for electronic equipment housing such as acrylic, ABS, polystyrene, PPO, polycarbonate, etc. You can
また、この発明において用いることのできる溶剤として
は、結合剤樹脂などの添加剤を溶解し、反応性の低い有
機溶剤が好ましい。例えば、トルエン、ヘキサン、キシ
レンなどの炭化水素類、メチルアルコール、エチルアル
コール、プロピルアルコール、ブチルアルコールなどの
アルコール類、メチルエチルケトン、メチルイソブチル
ケトンなどのケトン類、酢酸エチル、酢酸ブチルなどの
エステル類、メチルカルビトール、エチルカルビトー
ル、メチルセロソルブ、エチルセロソルブなどのエーテ
ル類などの有機溶剤の１種、または２種以上の混合物が
好ましい。As the solvent that can be used in the present invention, an organic solvent that dissolves an additive such as a binder resin and has low reactivity is preferable. For example, hydrocarbons such as toluene, hexane and xylene, alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, methyl One or a mixture of two or more organic solvents such as ethers such as carbitol, ethyl carbitol, methyl cellosolve and ethyl cellosolve is preferable.
銅粉、結合剤樹脂および溶剤からなる導電性組成物にお
けるジルコニウムアシレートポリマーおよび高級カルボ
ン酸エステルとの混合物の添加量は、溶剤分を除く導電
性組成物中において0.01〜15重量％、好ましくは、0.05
〜10重量％である。これは、0.05重量％未満では、銅粉
表面の改質が不十分となり、塗料の導電性、耐環境性お
よび塗膜の化学的、物理的強度が低下し始め、0.01重量
％未満では、その傾向が著しくなり、また、10重量％を
超えると銅粉表面に対し過剰となって改質を妨害し、塗
料の導電性、耐環境性および塗膜の化学的、物理的強度
が低下し始め、15重量％を超えると、その傾向が著しく
なるからである。Copper powder, the amount of the mixture of the zirconium acylate polymer and the higher carboxylic acid ester in the conductive composition consisting of the binder resin and the solvent is 0.01 to 15% by weight in the conductive composition excluding the solvent, preferably , 0.05
~ 10% by weight. This is because if it is less than 0.05% by weight, the modification of the copper powder surface becomes insufficient, and the electrical conductivity of the paint, the environment resistance and the chemical and physical strength of the coating film start to decrease, and if it is less than 0.01% by weight, the The tendency becomes remarkable, and when it exceeds 10% by weight, it becomes excessive on the surface of the copper powder and interferes with the modification, and the electrical conductivity of the paint, the environment resistance and the chemical and physical strength of the coating film start to deteriorate. If it exceeds 15% by weight, the tendency becomes remarkable.
上記の成分以外に、目的に応じて種々の添加剤を含める
ことができる。その様なものとして、還元剤、界面活性
剤、沈降防止剤、消泡剤、増粘剤、チクソトロピック
剤、防錆剤、難燃剤などある。In addition to the above components, various additives may be included depending on the purpose. Examples of such agents include reducing agents, surfactants, anti-settling agents, defoamers, thickeners, thixotropic agents, rust preventives, flame retardants and the like.
［作 用］ 上述の構成からなるこの発明および好ましい態様では、
次のように作用する。[Operation] In the present invention and the preferred embodiments having the above-mentioned configurations,
It works as follows.
この発明において、ジルコニウムアシレートポリマーと
高級カルボン酸エステルとの混合物で銅粉表面を被覆
し、銅粉の表面を改質する。詳細には、ジルコニウムア
シレートポリマーは、易加水分解性アルコキシ基と難加
水分解性かつ親油性のアシレート基と有するので、易加
水分解性アルコキシ基が銅粉表面もしくは被膜上の吸着
水と反応したり、静電的な接近により銅粉表面に結合
し、他方、親油性のアシレート基部分が銅粉の外側に配
向する。この親油性のアシレート基部分の膜は、銅粉表
面で疎水膜として作用し、更に、この親油性のアシレー
ト基部分は、導電性組成物中において、結合剤樹脂分子
とファンデルワールス力、水素結合、イオン結合、配位
結合、共有結合などにより巧みに絡み合い、攪拌、混練
工程時の剪断応力などによって塗料および塗膜中におけ
る銅粉の良好な分散状態を形成する。In this invention, the surface of the copper powder is modified by coating the surface of the copper powder with a mixture of a zirconium acylate polymer and a higher carboxylic acid ester. Specifically, since the zirconium acylate polymer has an easily hydrolyzable alkoxy group and a hardly hydrolyzable and lipophilic acylate group, the easily hydrolyzable alkoxy group reacts with the adsorbed water on the copper powder surface or the film. Or, they are bonded to the surface of the copper powder by electrostatic approach, while the lipophilic acylate group portion is oriented outside the copper powder. The film of the lipophilic acylate group part acts as a hydrophobic film on the surface of the copper powder, and further, the lipophilic acylate group part is a binder resin molecule and van der Waals force, hydrogen in the conductive composition. Cleverly entangled by a bond, an ionic bond, a coordinate bond, a covalent bond, etc., and a good dispersion state of the copper powder in the paint and the coating film is formed due to shear stress during stirring and kneading.
ジルコニウムアシレートポリマーの疎水膜が銅粉表面を
被覆するが、銅粉表面を完全に被覆することができず、
その膜に間隙や割れが生じる。高級カルボン酸エステル
は、易加水分解性アルコキシ基を有するので、銅粉表面
の吸着水とエステル交換反応をしたり、静電的な接近に
より銅粉表面に結合し、親油性のアシレート基部分によ
り、その間隙にカルボン酸エステルの疎水膜を形成して
銅粉表面に緻密な膜を形成する。また、ジルコニウムア
シレートポリマーと同様に、高級カルボン酸エステルの
親油性のアシレート基部分は、導電性組成物中におい
て、結合剤樹脂分子とファンデルワールス力、水素結
合、イオン結合、配位結合、共有結合などにより巧みに
絡み合い、攪拌、混練工程時の剪断応力などによって塗
料および塗膜中において銅粉をより良好な分散状態にす
る。The zirconium acylate polymer hydrophobic film covers the copper powder surface, but the copper powder surface cannot be completely covered,
Gaps and cracks occur in the film. Since the higher carboxylic acid ester has an easily hydrolyzable alkoxy group, it undergoes a transesterification reaction with the adsorbed water on the surface of the copper powder, or binds to the surface of the copper powder by electrostatic approach, so that the lipophilic acylate group part A hydrophobic film of carboxylic acid ester is formed in the gap to form a dense film on the surface of the copper powder. Further, like the zirconium acylate polymer, the lipophilic acylate group portion of the higher carboxylic acid ester has a binder resin molecule and a van der Waals force, a hydrogen bond, an ionic bond, a coordinate bond, in the conductive composition. Cleverly entangled by covalent bonds and the like, and makes the copper powder in a better dispersed state in the paint and coating film by shearing stress during stirring and kneading steps.
［発明の効果］ この発明により次の効果を発揮する。[Effects of the Invention] The present invention has the following effects.
請求項１の銅粉においては、ジルコニウムアシレートポ
リマーおよび高級カルボン酸エステルの混合物が被覆さ
れるので、銅粉表面または被膜上の吸着水と反応をした
り、静電的な接近などにより強固かつ導電性を損なわな
い膜を形成させることができる。従って、銅粉自体は、
良好な耐エージング性、防錆性、貯蔵安定性などを有す
る。Since the copper powder according to claim 1 is coated with the mixture of the zirconium acylate polymer and the higher carboxylic acid ester, the copper powder reacts with the adsorbed water on the surface of the copper powder or the coating film, and becomes strong due to electrostatic proximity. A film that does not impair conductivity can be formed. Therefore, the copper powder itself is
It has good aging resistance, rust resistance and storage stability.
請求項６の導電性塗料組成物においては、請求項１の被
覆された銅粉を含有するので、塗料の導電性、耐環境性
および貯蔵安定性が向上し、その塗膜の化学的、物理的
強度が改善されると共に、基材に対する密着強度が強く
なる。Since the conductive coating composition according to claim 6 contains the coated copper powder according to claim 1, the conductivity, environment resistance and storage stability of the coating are improved, and the chemical and physical properties of the coating film are improved. The mechanical strength is improved and the adhesion strength to the base material is increased.
請求項11の導電性塗料組成物においては、ジルコニウム
アシレートポリマーおよび高級カルボン酸エステルが、
銅粉を含む組成物に配合され、銅粉表面にそのポリマー
とエステルとの被膜が形成させる。したがって、請求項
６の導電性塗料組成物と同様に、この塗料の導電性、耐
環境性および貯蔵安定性、その塗膜の化学的、物理的強
度が改善されると共に、基材に対する密着強度を強くす
る。In the conductive coating composition according to claim 11, the zirconium acylate polymer and higher carboxylic acid ester,
It is blended with a composition containing copper powder to form a film of the polymer and ester on the surface of the copper powder. Therefore, similar to the conductive coating composition according to claim 6, the conductivity, environment resistance and storage stability of the coating, the chemical and physical strength of the coating film are improved, and the adhesion strength to the substrate is improved. Strengthen.
請求項16の製造法においては、分散浴によって個々の銅
粉の分散性を高めたり、流動性を変えることにより効率
的な表面改質、被覆ができ、銅粉自体の良好な耐エイジ
ング性、防錆性、貯蔵安定性などを最少の処理量で行う
ことができる。In the manufacturing method of claim 16, by increasing the dispersibility of each copper powder by a dispersion bath, or by changing the fluidity, efficient surface modification, coating can be performed, good aging resistance of the copper powder itself, Anticorrosion and storage stability can be achieved with the minimum processing amount.
［実施例］ この発明を、以下の例によつて説明する。[Examples] The present invention will be described with reference to the following examples.
実験材料 a.ジルコニウムアシレートポリマー（本発明） テトライソプロポキシジルコニウムまたはテトラｎ−ブ
トキシジルコニウム１モルと第１表に示す高級カルボン
酸を下記の割合で混合して反応させ、１−１〜８のジル
コニウムアシレートポリマーを得た。Experimental Materials a. Zirconium Acylate Polymer (Invention) 1 mol of tetraisopropoxyzirconium or tetra-n-butoxyzirconium was mixed with the higher carboxylic acid shown in Table 1 at the following ratios and reacted to give 1-1 to 8 A zirconium acylate polymer was obtained.
第１表 ポリマーNo. 高級カルボン酸 モル数 １−１ イソステアリン酸 ３ １−２ パルミチン酸 ３ １−３ ミスチリン酸 ４ １−４ ラウリン酸 ４ １−５ カプリン酸 ５ １−６ リノール酸 ５ １−７ オレイン酸 ６ １−８ リノレイン酸 ６ b.高級カルボン酸（本発明） 下記第２表に示す２−１〜８の高級カルボン酸エステル
を用いた。Table 1 Polymer No. Higher carboxylic acid Number of moles 1-1 Isostearic acid 3 1-2 Palmitic acid 3 1-3 Mistyric acid 4 1-4 Lauric acid 4 1-5 Capric acid 5 1-6 Linoleic acid 5 1-7 Oleic acid 6 1-8 Linoleic acid 6 b. Higher carboxylic acid (invention) The higher carboxylic acid esters 2-1 to 8 shown in Table 2 below were used.
第２表 エステルNo. 高級カルボン酸エステル ２−１ イソステアリン酸イソプロピル ２−２ パルミチン酸n-ブチル ２−３ ミスチリン酸イソブチル ２−４ ラウリン酸イソプロピル ２−５ カプリン酸t-ブチル ２−６ リノール酸イソプロピル ２−７ オレイン酸n-ブチル ２−８ リノレイン酸t-ブチル c.金属有機化合物（比較） 比較のために、下記の第３表の金属有機化合物を用い
た。Table 2 Ester No. Higher carboxylic acid ester 2-1 Isopropyl isostearate 2-2 n-Butyl palmitate 2-3 Isobutyl mystyriate 2-4 Isopropyl laurate 2-5 t-Butyl caprate 2-6 Isopropyl linoleate 2-7 n-Butyl oleate 2-8 t-Butyl linoleate c. Metal Organic Compounds (Comparative) For comparison, the metal organic compounds shown in Table 3 below were used.
d.低級カルボン酸 比較のために用いた低級カルボン酸は、第４表に示す通
りである。 d. Lower carboxylic acid The lower carboxylic acid used for comparison is shown in Table 4.
第４表 No. 低級カルボン酸 ４−１… イソ酪酸イソプロピル ４−２… 吉草酸イソプロピル ４−３… カプロン酸n-ブチル ４−４… 酢酸エチル e.ジルコニウムアシレートポリマーと高級カルボン酸エ
ステルとの混合物（本発明） 第１表のジルコニウムアシレートポリマーと第２表の高
級カルボン酸エステルとを第５表に示す組合わせおよび
組成でこの発明による混合物を調製した。Table 4 No. Lower carboxylic acid 4-1 Isopropyl isobutyrate 4-2 Isopropyl valerate 4-3 n-Butyl caproate 4-4 Ethyl acetate e. Zirconium acylate polymer and higher carboxylic acid ester Mixtures (Invention) Mixtures according to the invention were prepared with the combinations and compositions shown in Table 5 of the zirconium acylate polymers of Table 1 and the higher carboxylic acid esters of Table 2.
f.比較のための金属有機化合物と低級カルボン酸エステ
ルとの混合物 第３表の金属有機化合物と第４表のカルボン酸エステル
とを第６表に示す組合わせおよび組成でこの比較のため
の混合物を調製した。 f. Mixture of metal organic compound and lower carboxylic acid ester for comparison Mixture for this comparison in the combination and composition shown in Table 6 of the metal organic compound of Table 3 and the carboxylic acid ester of Table 4 Was prepared.
g.銅粉 第７表に示す樹枝状電解銅粉（三井金属鉱業株式会社
製、MF−D2）を用いた。 g. Copper powder The dendritic electrolytic copper powder shown in Table 7 (MF-D2 manufactured by Mitsui Mining & Smelting Co., Ltd.) was used.
第７表 見掛密度 0.8〜1.1g/cm3 比表面積 0.40m2/g 純度 99.2％以上 HNO3不溶解分 0.03％未満 還元減量 0.80％未満 平均粒径 8.0μｍ 実験例１ 防錆効果 第７表に示した銅粉を、トルエン溶媒中で攪拌分散させ
て、第５表および第６表で示す混合物（サンプルNo5−
１〜24およびNo6−１〜12）を銅粉分散浴中に少量ずつ
添加して銅粉を処理した。銅粉を乾燥させた後に、85℃
の温度、60℃/95％RHの湿度環境で、2000時間放置して
耐熱、耐湿の試験をした。なお、各混合物の処理量は、
各々、0.01、0.1、0.5、1.0、5.0、10.0重量％であっ
た。Table 7 Apparent density 0.8-1.1g / cm 3 Specific surface area 0.40m 2 / g Purity 99.2% or more HNO 3 insoluble matter less than 0.03% Reduction weight reduction less than 0.80% Average particle size 8.0μm Experimental example 1 Rust prevention effect No. 7 The copper powder shown in the table was stirred and dispersed in a toluene solvent, and the mixture shown in Table 5 and Table 6 (Sample No.
1 to 24 and Nos. 6-1 to 12) were added little by little to the copper powder dispersion bath to treat the copper powder. 85 ℃ after drying the copper powder
In a humidity environment of 60 ° C / 95% RH, the sample was left to stand for 2000 hours for heat resistance and humidity resistance test. The throughput of each mixture is
The amounts were 0.01, 0.1, 0.5, 1.0, 5.0 and 10.0% by weight, respectively.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉では、
全く変色がなく、緑青の発生がなかった。As a result, in the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24, and the treatment amount was 0.1 to 10% by weight,
There was no discoloration and no patina.
他方、比較の混合物サンプルNo6−１〜12で処理された
銅粉は、茶褐色の変色が見られ、緑青の発生もあった。
以上の結果からこの発明による銅粉は、形成された疎水
膜が緻密であり、防錆効果および耐環境性に優れている
ことを分かった。On the other hand, the copper powders treated with the comparative mixture sample Nos. 6-1 to 12 exhibited brownish discoloration and generation of patina.
From the above results, it was found that the copper powder according to the present invention has a dense hydrophobic film formed, and is excellent in rust prevention effect and environment resistance.
実験例２ 塗料の体積固有抵抗と耐環境性（イ） 実験例１で用いた表面被覆処理銅粉を、銅粉に対して45
重量％のメタクリル系樹脂溶液（アクリボンド〜BC−41
5B、三菱レーヨン製）および溶剤（トルエン）と共に攪
拌し、導電塗料を調製した。得られた導電塗料をスクリ
ーン印刷機でアクリル板上に回路を形成して25℃、24時
間、大気中で乾燥した。この回路について体積固有抵抗
を測定した。Experimental Example 2 Volume resistivity and environmental resistance of paint (a) The surface-coated copper powder used in Experimental Example 1 was used in an amount of 45
Wt% methacrylic resin solution (Acrybonad to BC-41
5B, manufactured by Mitsubishi Rayon) and stirred with a solvent (toluene) to prepare a conductive paint. A circuit was formed on the acrylic plate of the obtained conductive paint by a screen printing machine, and dried at 25 ° C. for 24 hours in the atmosphere. The volume resistivity of this circuit was measured.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉から得
られた導電塗料は、３×10-4〜６×10-4Ω・cmの体積固
有抵抗を有した。他方、比較の混合物サンプルNo6−１
〜12で処理された銅粉銅粉から得られた導電塗料は、２
×10-3〜５×10-3Ω・cmの体積固有抵抗を示した。As a result, the conductive paint obtained from the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24 and the treatment amount was from 0.1 to 10% by weight, was 3 × 10 −4 to 6 × 10 −4 Ω ·. It had a volume resistivity of cm. On the other hand, comparative mixture sample No6-1
Copper powder treated with ~ 12 conductive paint obtained from copper powder is 2
It exhibited a volume resistivity of × 10 -3 to 5 × 10 -3 Ω · cm.
この発明による銅粉は導電性を損なわないことがこの結
果から判明した。From this result, it was found that the copper powder according to the present invention does not impair the conductivity.
上記の導電塗料を、20〜25℃/60〜70％RHの環境で、３
ケ月間放置して体積固有抵抗を同様に測定した。Apply the above conductive paint in an environment of 20-25 ° C / 60-70% RH for 3
The sample was left for a month and the volume resistivity was measured in the same manner.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉から得
られた導電塗料は、３×10-4〜６×10-4Ω・cmの体積固
有抵抗を有した。他方、比較の混合物サンプルNo6−１
〜12で処理された銅粉銅粉から得られた導電塗料は、銅
粉と樹脂や溶剤との分離状態が激しく、銅粉が固化して
塗料化が不可能であった。As a result, the conductive paint obtained from the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24 and the treatment amount was from 0.1 to 10% by weight, was 3 × 10 −4 to 6 × 10 −4 Ω ·. It had a volume resistivity of cm. On the other hand, comparative mixture sample No6-1
In the conductive paint obtained from the copper powder treated with ~ 12, the copper powder was severely separated from the resin and the solvent, and the copper powder was solidified so that it could not be made into a paint.
これらの結果より、この発明による銅粉から調製された
導電塗料は、優れた導電性と耐環境性を有していること
が判った。From these results, it was found that the conductive paint prepared from the copper powder according to the present invention had excellent conductivity and environment resistance.
実験例３ 塗料の体積固有抵抗と耐環境性（ロ） 第７表の未被覆銅粉と、銅粉に対して45重量％のメタク
リル系樹脂溶液（アクリボンド〜BC−415B、三菱レーヨ
ン製）と、銅粉および樹脂固形分に対し混合物サンプル
No5−１〜24および比較の混合物サンプルNo6−１〜12
を、各々0.05、0.1、0.5、1.0、5.1、10.0重量％と、溶
剤（トルエン）とを攪拌し、導電塗料を調製した。得ら
れた導電塗料をスクリーン印刷機でアクリル板上に回路
を形成して25℃、24時間、大気中で乾燥した。この回路
について体積固有抵抗を測定した。Experimental Example 3 Volume resistivity and environmental resistance of coating material (b) Uncoated copper powder shown in Table 7 and a methacrylic resin solution of 45% by weight with respect to the copper powder (Akribbon-BC-415B, manufactured by Mitsubishi Rayon) Mixture samples for copper powder and resin solids
No 5-1 to 24 and comparative mixture sample Nos 6-1 to 12
Were mixed with 0.05, 0.1, 0.5, 1.0, 5.1, 10.0% by weight and a solvent (toluene) to prepare a conductive paint. A circuit was formed on the acrylic plate of the obtained conductive paint by a screen printing machine, and dried at 25 ° C. for 24 hours in the atmosphere. The volume resistivity of this circuit was measured.
その結果、混合物サンプルNo5−１〜24が添加されたこ
の発明の導電塗料は、３×10-4〜６×10-4Ω・cmの体積
固有抵抗を有した。他方、比較の混合物サンプルNo6−
１〜12が添加された比較の導電塗料は、２×10-3〜５×
10-3Ω・cmの体積固有抵抗を示した。As a result, the conductive paint of the present invention to which the mixture sample Nos. 5-1 to 24 were added had a volume resistivity of 3 × 10 −4 to 6 × 10 −4 Ω · cm. On the other hand, comparative mixture sample No6 −
Comparative conductive paint containing 1 to 12 is 2 × 10 −3 to 5 ×
It exhibited a volume resistivity of 10 -3 Ω · cm.
上記の導電塗料を、20〜25℃/60〜70％RHの環境で、３
ケ月間放置して体積固有抵抗を同様に測定した。Apply the above conductive paint in an environment of 20-25 ° C / 60-70% RH for 3
The sample was left for a month and the volume resistivity was measured in the same manner.
その結果、混合物サンプルNo5−１〜24が添加されたこ
の発明による導電塗料は、３×10-4〜６×10-4Ω・cmの
体積固有抵抗を有した。他方、比較の混合物サンプルNo
6−１〜12が添加された導電塗料は、銅粉と樹脂や溶剤
との分離状態が激しく、銅粉が固化して塗料化が不可能
であった。As a result, the conductive paint according to the present invention to which the mixture sample Nos. 5-1 to 24 were added had a volume resistivity of 3 × 10 −4 to 6 × 10 −4 Ω · cm. On the other hand, the comparative mixture sample No.
In the conductive paint to which 6-1 to 12 were added, the copper powder was severely separated from the resin and the solvent, and the copper powder was solidified so that it could not be made into a paint.
これらの結果より、この発明による銅粉から調製された
導電塗料は、優れた導電性と耐環境性を有していること
が判った。From these results, it was found that the conductive paint prepared from the copper powder according to the present invention had excellent conductivity and environment resistance.
実験例４ 塗膜の耐熱耐湿エージング性 実験例２および３と同様にしてアクリル板上に導体回路
を形成し、85℃の耐熱試験、60℃/95％RHの耐湿試験
で、2000時間放置して抵抗変化率（％）を測定した。Experimental Example 4 Heat and moisture resistance aging resistance of coating film A conductor circuit was formed on an acrylic plate in the same manner as in Experimental Examples 2 and 3, and left for 2000 hours in a heat resistance test at 85 ° C and a humidity resistance test at 60 ° C / 95% RH. Resistance change rate (%) was measured.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉から得
られた導電塗料の塗膜および、混合物サンプルNo5−１
〜24が添加されたこの発明の導電塗料の塗膜は、85℃の
耐熱試験においては、殆どが８％前後、少なくて５％、
多くても15％に過ぎない変化率を示した。また、60℃/9
5％RHの耐湿試験においては、殆どが５％前後、少なく
て−10％、多くても８％に過ぎない変化率を示した。As a result, the coating film of the conductive paint obtained from the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24 and the treatment amount was 0.1 to 10% by weight, and the mixture sample No. 5-1.
In the heat resistance test at 85 ° C, most of the coating films of the conductive paint of the present invention to which ~ 24 is added are around 8%, at least 5%,
The rate of change was only 15% at most. Also, 60 ° C / 9
In a humidity resistance test at 5% RH, most of them showed a change rate of around 5%, at least -10%, and at most 8%.
これに対して、比較の混合物サンプルNo6−１〜12で処
理された銅粉から得られた導電塗料の塗膜および、比較
の混合物サンプルNo6−１〜12が添加された比較の導電
塗料の塗膜は、85℃の耐熱試験においては、多くが70〜
100％の変化率を示し、少なからず150％の変化率を示し
た。また、60℃/95％RHの耐湿試験においては、多くが5
0〜70％の変化率を示し、少なからず100％の変化率を示
した。On the other hand, a coating of the conductive paint obtained from the copper powder treated with the comparative mixture sample Nos. 6-1 to 12 and a coating of the comparative conductive paint with the addition of the comparative mixture sample Nos. 6-1 to 12 In the heat resistance test at 85 ° C, most of the films are 70 ~
The rate of change was 100%, and not less than 150%. In addition, in the humidity test of 60 ℃ / 95% RH, most of the
The rate of change was 0-70%, and not a little 100%.
これらのことから、この発明による導電塗料およびその
塗膜は、耐熱、耐湿エージング性において著しく優れて
いることがわかる。From these facts, it is understood that the conductive coating material and the coating film thereof according to the present invention are remarkably excellent in heat resistance and humidity aging resistance.
実験例５ 塗膜の耐塩水性 実験例２および３と同様にしてアクリル板上に導体回路
を形成し、塩水噴霧試験を行った。塩水噴霧試験はJIS
規格に基き、塩水濃度５重量％の水溶液（液温35℃）を
用い、噴霧から72時間後の塗膜表面の緑青の発生を観察
した。Experimental Example 5 Salt Water Resistance of Coating Film In the same manner as in Experimental Examples 2 and 3, a conductor circuit was formed on an acrylic plate and a salt spray test was conducted. JIS for salt spray test
Based on the standard, an aqueous solution having a salt water concentration of 5% by weight (liquid temperature 35 ° C.) was used, and generation of patina on the surface of the coating film was observed 72 hours after spraying.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉から得
られた導電塗料の塗膜および、混合物サンプルNo5−１
〜24が添加されたこの発明の導電塗料の塗膜では、全く
緑青の発生が見られなかった。As a result, the coating film of the conductive paint obtained from the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24 and the treatment amount was 0.1 to 10% by weight, and the mixture sample No. 5-1.
In the coating film of the conductive paint of the present invention to which ~ 24 was added, no generation of patina was observed.
比較の混合物サンプルNo6−１〜12で処理された銅粉銅
粉から得られた導電塗料の塗膜および、比較の混合物サ
ンプルNo6−１〜12が添加された比較の導電塗料の塗膜
では、塗膜全面に激しく緑青が見られた。In the coating film of the conductive paint obtained from the copper powder copper powder treated with the comparative mixture sample No6-1 to 12, and the conductive paint film of the comparative mixture to which the comparative mixture sample No6-1 to 12 was added, There was intense patina on the entire surface of the coating film.
これらのことから、この発明による導電塗料およびその
塗膜は、優れた耐塩水性を有することが判った。From these, it was found that the conductive paint and the coating film according to the present invention have excellent salt water resistance.
実験例６ 塗膜の密着性 実験例２および３で調製された導電塗料を、アクリル板
にスクリーン印刷機により、２×2mmパッド塗膜を形成
し、塗膜の乾燥後に75℃/60分、−55℃/60分の条件で10
0サイクルのヒートショック試験をし、次いで、塗膜上
に常温硬化型エポキシ樹脂を用いて0.5φmmスズ鍍金銅
線を接着して90゜プール試験を行った。塗膜の厚さは、
70±20μｍであり、試験パッド数は20個であった。Experimental Example 6 Adhesion of coating film The conductive paint prepared in Experimental Examples 2 and 3 was used to form a 2 × 2 mm pad coating film on an acrylic plate by a screen printing machine, and after drying the coating film, 75 ° C./60 minutes, 10 at -55 ° C / 60 minutes
A 0-cycle heat shock test was performed, and then a 0.5φ mm tin-plated copper wire was adhered to the coating film using a room temperature curing type epoxy resin to perform a 90 ° pool test. The thickness of the coating film is
It was 70 ± 20 μm, and the number of test pads was 20.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉から得
られた導電塗料のパッド塗膜および、混合物サンプルNo
5−１〜24が添加されたこの発明の導電塗料のパッド塗
膜における剥離強度は、0.8〜1.0kg/mm2であった。As a result, the pad coating film of the conductive paint obtained from the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24 and the treatment amount was 0.1 to 10% by weight, and the mixture sample No.
The peel strength of the conductive coating material of the present invention containing 5-1 to 24 added thereto was 0.8 to 1.0 kg / mm 2 .
他方、比較の混合物サンプルNo6−１〜12で処理された
銅粉銅粉から得られた導電塗料のパッド塗膜および、比
較の混合物サンプルNo6−１〜12が添加された比較の導
電塗料のパッド塗膜における剥離強度は、0.4〜0.6kg/m
m2にすぎなっかた。On the other hand, a pad coating of a conductive paint obtained from copper powder copper powder treated with the comparative mixture sample Nos 6-1 to 12, and a pad of a comparative conductive paint to which the comparative mixture sample Nos 6-1 to 12 are added. The peel strength of the coating film is 0.4-0.6kg / m
It was only m 2 .
この結果より、この発明の導電塗料の塗膜は、優れた基
材に対する密着性を有することが判った。From this result, it was found that the coating film of the conductive coating material of the present invention had excellent adhesion to the substrate.
実験例７ 塗膜の密着性 実験例２および３で調製された導電塗料を、フェノール
板、ガラスエポキシ板およびABS板にスクリーン印刷機
により、２×2mmパッド塗膜と形成し、塗膜の乾燥後
に、塗膜上に常温硬化型エポキシ樹脂を用いて0.5φmm
スズ鍍金銅線を接着して90゜プール試験を行った。塗膜
の厚さは、70±20μｍであり、試験パッド数は20個であ
った。Experimental Example 7 Adhesion of coating film The conductive coating material prepared in Experimental Examples 2 and 3 was formed into a 2 x 2 mm pad coating film on a phenol plate, a glass epoxy plate and an ABS plate by a screen printing machine, and the coating film was dried. After that, use a room temperature curing type epoxy resin on the coating film to give a diameter of 0.5 mm
A 90 ° pool test was conducted by bonding a tin-plated copper wire. The thickness of the coating film was 70 ± 20 μm, and the number of test pads was 20.
その結果、混合物サンプルNo5−１〜24で処理され、処
理量が0.1〜10重量％であるこの発明による銅粉から得
られた導電塗料のパッド塗膜および、混合物サンプルNo
5−１〜24が添加されたこの発明の導電塗料のパッド塗
膜のフェノール板、ガラスエポキシ板およびABS板に対
する剥離強度は、0.8〜1.2kg/mm2であった。As a result, the pad coating film of the conductive paint obtained from the copper powder according to the present invention, which was treated with the mixture sample Nos. 5-1 to 24 and the treatment amount was 0.1 to 10% by weight, and the mixture sample No.
The peeling strength of the pad coating film of the conductive paint of the present invention to which 5-1 to 24 were added was 0.8 to 1.2 kg / mm 2 with respect to the phenol plate, the glass epoxy plate and the ABS plate.
他方、比較の混合物サンプルNo6−１〜12で処理された
銅粉銅粉から得られた導電塗料のパッド塗膜および、比
較の混合物サンプルNo6−１〜12が添加された比較の導
電塗料のパッド塗膜のフェノール板、ガラスエポキシ板
およびABS板に対する剥離強度は、0.4〜0.6kg/mm2にす
ぎなっかた。On the other hand, a pad coating of a conductive paint obtained from copper powder copper powder treated with the comparative mixture sample Nos 6-1 to 12, and a pad of a comparative conductive paint to which the comparative mixture sample Nos 6-1 to 12 are added. The peel strength of the coating film to the phenol plate, glass epoxy plate and ABS plate was only 0.4 to 0.6 kg / mm 2 .
この結果より、この発明の導電塗料の塗膜は、種々の基
材に対する優れた密着性を有することが判った。From this result, it was found that the coating film of the conductive coating material of the present invention has excellent adhesion to various base materials.
実験例８ 塗膜の断面観察 実験例６および７で形成したパッド塗膜を走査型電子顕
微鏡（700倍）で観察した。Experimental Example 8 Cross-section observation of coating film The pad coating film formed in Experimental Examples 6 and 7 was observed with a scanning electron microscope (700 times).
その結果、この発明による導電塗料の塗膜の断面は、第
１図の写真に示すように、銅粉の片寄りが全く無く、塗
膜中の結合剤樹脂と基剤が確実に密着していた。As a result, as shown in the photograph of FIG. 1, the cross section of the coating film of the conductive paint according to the present invention showed no deviation of the copper powder, and the binder resin and the base in the coating film were surely adhered. It was
他方、比較の導電塗料の塗膜の断面は、第２図の写真に
示すように、銅粉が片寄り、塗膜中の結合剤樹脂と基材
に隙間が観察された。On the other hand, in the cross section of the coating film of the comparative conductive paint, as shown in the photograph of FIG. 2, the copper powder was offset, and a gap was observed between the binder resin in the coating film and the substrate.
実験例９ 導電性（イ） 第７表の未被覆銅粉と銅粉に対して45重量％のフェノー
ル系樹脂（PL-2210、固形分:60重量％〜群栄化学工業
製）と、銅粉および樹脂固形分に対し混合物サンプルNo
5−１〜24および比較の混合物サンプルNo6−１〜12を、
各々0.05,0.1,0.5,1.0,5.0,10.0重量％と、溶剤（メチ
ルカルビトール）を混練し、導電塗料を調整した。得ら
れた導電塗料をスクリーン印刷機でフェノール板上に回
路を形成して150℃、30分間、大気中で硬化した。この
回路について体積固有抵抗を測定した。Experimental Example 9 Conductivity (a) Uncoated copper powder shown in Table 7 and 45% by weight of phenolic resin (PL-2210, solid content: 60% by weight to Gunei Chemical Industry Co., Ltd.) based on copper powder, and copper Mixture sample No. for powder and resin solids
5-1 to 24 and comparative mixture sample No. 6-1 to 12,
0.05, 0.1, 0.5, 1.0, 5.0, 10.0% by weight of each and a solvent (methyl carbitol) were kneaded to prepare a conductive paint. A circuit was formed on the phenol plate by a screen printing machine, and the obtained conductive paint was cured in air at 150 ° C. for 30 minutes. The volume resistivity of this circuit was measured.
その結果、混合物サンプルNo5−１〜24が添加されたこ
の発明の導電塗料は３×10-4〜６×10-4Ω・cmの体積固
有抵抗を有した。他方、比較の混合物サンプルNo6−１
〜12が添加された比較の導電塗料は、２×10-3〜５×10
-3Ω・cmの体積固有抵抗を示した。As a result, the conductive paint of the present invention to which the mixture sample Nos. 5-1 to 24 were added had a volume resistivity of 3 × 10 −4 to 6 × 10 −4 Ω · cm. On the other hand, comparative mixture sample No6-1
Comparative conductive paint with ~ 12 added is 2 x 10 -3 to 5 x 10
It exhibited a volume resistivity of -3 Ω · cm.
これらの結果により、この発明による導電塗料は優れた
導電性を有していることが判った。From these results, it was found that the conductive paint according to the present invention has excellent conductivity.
実験例10 導電性（ロ） 置換メッキ法により銀が５重量％被覆された第７表の銅
粉と銅粉に対して45重量％のメタクリル系樹脂溶液（ア
クリボンド〜BC−415B、三菱レーヨン製）と、銅粉およ
び固形分に対し混合物サンプルNo5−１〜24および比較
の混合物サンプルNo6−１〜12を各々0.05,0.1,0.5,1.0,
5.0,10.0重量％と溶剤（トルエン）を攪拌し、導電塗料
を調整した。得られた導電塗料をスクリーン印刷機でア
クリル板上に回路を形成して25℃、24時間、大気中で乾
燥しした。この回路について体積固有抵抗を測定した。Experimental Example 10 Conductivity (b) Copper powder coated with 5% by weight of silver by the displacement plating method and 45% by weight of a methacrylic resin solution with respect to the copper powder (Acribonad to BC-415B, manufactured by Mitsubishi Rayon Co., Ltd. ), And copper powder and solids mixture sample No 5-1 to 24 and comparative mixture sample No 6-1 to 0.05, 0.1, 0.5, 1.0, respectively.
5.0, 10.0% by weight and a solvent (toluene) were stirred to prepare a conductive paint. A circuit was formed on the acrylic plate of the obtained conductive paint by a screen printing machine, and dried at 25 ° C. for 24 hours in the atmosphere. The volume resistivity of this circuit was measured.
その結果、混合物サンプルNo5−１〜24が添加されたこ
の発明の導電塗料は、２×10-4〜４×10-4Ω・cmの体積
固有抵抗を有した。他方、比較の混合物サンプルNo6−
１〜12が添加された比較の導電塗料は、２×10-3〜５×
10-3Ω・cmの体積固有抵抗を示した。As a result, the conductive coating material of the present invention to which the mixture sample Nos. 5-1 to 24 were added had a volume resistivity of 2 × 10 −4 to 4 × 10 −4 Ω · cm. On the other hand, comparative mixture sample No6 −
Comparative conductive paint containing 1 to 12 is 2 × 10 −3 to 5 ×
It exhibited a volume resistivity of 10 -3 Ω · cm.
これらの結果より、この発明による導電塗料は優れた導
電性を有していることが判った。From these results, it was found that the conductive paint according to the present invention has excellent conductivity.
実験例11 塗膜の耐熱性 実験例１で用いた被膜銅粉を、銅粉に対して45重量％の
フェノール系樹脂（PL-2210、固形分:60重量％〜群栄化
学工業製）と溶剤（メチルカルビトール）とに混練し、
導電性塗料を調製した。得られた導電性塗料からスクリ
ーン印刷機でフェノール板上に回路（塗膜）を形成して
150℃、30分間、大気中で硬化した。この回路を、240℃
のSn63/Pb37半田槽に５秒間、10サイクル浸漬し、抵抗
変化率（％）を測定した。Experimental Example 11 Heat resistance of coating film The coated copper powder used in Experimental Example 1 was mixed with 45% by weight of a phenolic resin (PL-2210, solid content: 60% by weight to Gunei Chemical Industry Co., Ltd.) based on the copper powder. Knead with a solvent (methyl carbitol),
A conductive paint was prepared. Form a circuit (coating film) on the phenol plate with a screen printer from the conductive paint obtained.
Cured in air at 150 ° C for 30 minutes. This circuit, 240 ℃
Was immersed in a Sn63 / Pb37 solder bath for 5 seconds for 10 cycles, and the resistance change rate (%) was measured.
その結果、混合物サンプルNo5−１〜24を用いて得たこ
の発明の導電性塗料（使用量0.1〜10重量％）から得ら
れた回路では、全く変色もせず、殆どが５％前後、少な
くて−６％、多くて８％の変化率を示すに過ぎなかっ
た。As a result, in the circuit obtained from the conductive coating material of the present invention (use amount 0.1 to 10% by weight) obtained by using the mixture sample Nos. 5-1 to 24, there was no discoloration at all, and most of them were around 5% and small. It showed a rate of change of -6%, at most 8%.
これに対して、比較の混合物サンプルNo6−１〜12を用
いて得た導電性塗料から得られた回路では、塗膜が著し
く変色し、多くが50％以上、少なからず150％以上の変
化率を示した。On the other hand, in the circuit obtained from the conductive paint obtained by using the comparative mixture sample Nos. 6-1 to 12, the coating film was significantly discolored, and the change rate was 50% or more, not less than 150%. showed that.
これらの結果より、この発明による導電性塗料の塗膜は
優れた耐熱性を有していることが判った。From these results, it was found that the coating film of the conductive paint according to the present invention has excellent heat resistance.
第１図は、この発明による導電塗料の塗膜断面中の銅粉
の粒子構造を示す電子顕微鏡写真、第２図は、比較例に
よる導電塗料の塗膜断面中の銅粉の粒子構造を示す電子
顕微鏡写真である。FIG. 1 is an electron micrograph showing a particle structure of copper powder in a coating film cross section of a conductive paint according to the present invention, and FIG. 2 shows a particle structure of copper powder in a conductive paint film cross section of a comparative example. It is an electron micrograph.
Claims (14)
リマーと高級カルボン酸エステルとの混合物が被覆され
たことを特徴とする導電塗料用銅粉。1. A copper powder for a conductive coating, characterized in that the surface of the copper powder is coated with a mixture of a zirconium acylate polymer and a higher carboxylic acid ester.
シレート基と、易加水分解性アルコキシ基とからなる請
求項１に記載の導電塗料用銅粉。2. The copper powder for a conductive coating according to claim 1, wherein the higher carboxylic acid ester comprises a higher fatty acid acylate group and an easily hydrolyzable alkoxy group.
返し単位Ｉ、IIおよび／またはIIIからなる請求項１ま
たは２に記載の導電塗料用銅粉。 （式中、Ｒ、R1、R2およびR3は、同種または異種の炭素
数１〜25の炭化水素基である）3. The copper powder for a conductive coating according to claim 1, wherein the zirconium acylate polymer comprises the following repeating units I, II and / or III. (In the formula, R, R 1 , R 2 and R 3 are the same or different hydrocarbon groups having 1 to 25 carbon atoms)
ルボン酸エステルとの混合比が、ジルコニウムアシレー
トポリマー10〜90重量％に対して高級カルボン酸エステ
ル90〜10重量％である請求項１、２または３に記載の導
電塗料用銅粉。4. The mixing ratio of the zirconium acylate polymer and the higher carboxylic acid ester is 90 to 10% by weight of the higher carboxylic acid ester with respect to 10 to 90% by weight of the zirconium acylate polymer. Copper powder for conductive paint according to.
ルボン酸エステルとの混合物の銅粉に対する被覆量が、
0.05〜10重量％である請求項１〜４のいずれか１項に記
載の導電塗料用銅粉。5. A coating amount of a mixture of a zirconium acylate polymer and a higher carboxylic acid ester with respect to copper powder,
It is 0.05-10 weight%, The copper powder for conductive paints of any one of Claims 1-4.
剤樹脂と、溶剤とを含む導電性塗料組成物。6. A conductive coating composition containing the copper powder for conductive coating according to claim 1, a binder resin, and a solvent.
のジルコニウム原子に結合した易加水分解性アルコキシ
基と、同じくジルコニウム原子に結合した難加水分解性
かつ親油性のアシレート基とを有する請求項６に記載の
導電性塗料組成物。7. A zirconium acylate polymer having an easily hydrolyzable alkoxy group bonded to a zirconium atom of the main chain and a hardly hydrolyzable and lipophilic acylate group also bonded to a zirconium atom. The conductive coating composition as described above.
シレート基と、易加水分解性アルコキシ基とからなる請
求項６に記載の導電性塗料組成物。8. The conductive coating composition according to claim 6, wherein the higher carboxylic acid ester comprises a higher fatty acid acylate group and an easily hydrolyzable alkoxy group.
ルボン酸エステルとの混合比が、ジルコニウムアシレー
トポリマー10〜90重量％に対して高級カルボン酸エステ
ル90〜10重量％である請求項６、７または８に記載の導
電性塗料組成物。9. The mixing ratio of the zirconium acylate polymer to the higher carboxylic acid ester is 90 to 10% by weight of the higher carboxylic acid ester with respect to 10 to 90% by weight of the zirconium acylate polymer. The electrically conductive coating composition according to.
カルボン酸エステルとの混合物の銅粉に対する被覆量
が、0.05〜10重量％である請求項６〜９のいずれか１項
に記載の導電性塗料組成物。10. The conductive coating composition according to claim 6, wherein the coating amount of the mixture of the zirconium acylate polymer and the higher carboxylic acid ester with respect to the copper powder is 0.05 to 10% by weight. .
トポリマーと高級カルボン酸エステルとの混合物を添加
して銅粉の表面にジルコニウムアシレートポリマーおよ
び高級カルボン酸エステルの被膜を形成し、必要に応じ
て分散媒を除去し、導電塗料用銅粉を得ることを含む導
電塗料用銅粉の製造法。11. A mixture of a zirconium acylate polymer and a higher carboxylic acid ester is added to a copper powder dispersion bath to form a film of the zirconium acylate polymer and a higher carboxylic acid ester on the surface of the copper powder. According to the method, a dispersion medium is removed to obtain a copper powder for conductive paint, and a method for producing copper powder for conductive paint.
カルボン酸エステルとの混合物が、テトラアルコキシジ
ルコニウムと高級カルボン酸との反応混合物である、請
求項11に記載の導電塗料用銅粉の製造法。12. The method for producing copper powder for a conductive coating according to claim 11, wherein the mixture of the zirconium acylate polymer and the higher carboxylic acid ester is a reaction mixture of tetraalkoxy zirconium and the higher carboxylic acid.
数１〜10のアルキル基を有する請求項11に記載の導電塗
料用銅粉の製造法。13. The method for producing a copper powder for a conductive coating according to claim 11, wherein the tetraalkoxyzirconium has an alkyl group having 1 to 10 carbon atoms.
剤である請求項11に記載の導電塗料用銅粉の製造法。14. The method for producing a copper powder for a conductive coating according to claim 11, wherein the dispersion medium is water or an organic solvent that can be easily removed.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63027235A JPH0670193B2 (en) | 1988-02-08 | 1988-02-08 | Copper powder for conductive paint and its manufacturing method |
| CA000574830A CA1337545C (en) | 1988-02-01 | 1988-08-16 | Copper powder for electroconductive paints and electroconductive paint compositions |
| US07/232,669 US5068150A (en) | 1988-02-01 | 1988-08-16 | Copper powder for electroconductive paints and electroconductive paint compositions |
| EP88307665A EP0326737B1 (en) | 1988-02-01 | 1988-08-18 | Copper powder for electroconductive paints and electroconductive paint compositions |
| DE8888307665T DE3872697T2 (en) | 1988-02-01 | 1988-08-18 | COPPER POWDER FOR CONDUCTIVE COATINGS AND CONDUCTIVE COATING MEASURES. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63027235A JPH0670193B2 (en) | 1988-02-08 | 1988-02-08 | Copper powder for conductive paint and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01203479A JPH01203479A (en) | 1989-08-16 |
| JPH0670193B2 true JPH0670193B2 (en) | 1994-09-07 |
Family
ID=12215412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63027235A Expired - Lifetime JPH0670193B2 (en) | 1988-02-01 | 1988-02-08 | Copper powder for conductive paint and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0670193B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10126028A (en) * | 1996-10-22 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Printed board |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02190402A (en) * | 1989-01-19 | 1990-07-26 | Dowa Mining Co Ltd | Metal powder having high oxidation resistance and production thereof |
-
1988
- 1988-02-08 JP JP63027235A patent/JPH0670193B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10126028A (en) * | 1996-10-22 | 1998-05-15 | Matsushita Electric Ind Co Ltd | Printed board |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01203479A (en) | 1989-08-16 |
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