JPH0368702A - Method for treating surface of copper powder - Google Patents
Method for treating surface of copper powderInfo
- Publication number
- JPH0368702A JPH0368702A JP1205344A JP20534489A JPH0368702A JP H0368702 A JPH0368702 A JP H0368702A JP 1205344 A JP1205344 A JP 1205344A JP 20534489 A JP20534489 A JP 20534489A JP H0368702 A JPH0368702 A JP H0368702A
- Authority
- JP
- Japan
- Prior art keywords
- copper powder
- metal
- metal alkoxide
- solvent
- compound
- 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.)
- Pending
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 24
- -1 acylate compound Chemical class 0.000 claims abstract description 23
- 238000004381 surface treatment Methods 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 4
- 229930195729 fatty acid Natural products 0.000 claims abstract description 4
- 239000000194 fatty acid Substances 0.000 claims abstract description 4
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract 2
- 229910052738 indium Inorganic materials 0.000 claims abstract 2
- 229910052745 lead Inorganic materials 0.000 claims abstract 2
- 229910052710 silicon Inorganic materials 0.000 claims abstract 2
- 229910052718 tin Inorganic materials 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 21
- 239000002904 solvent Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 241001311547 Patina Species 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical class CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 150000001875 compounds Chemical class 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-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
- 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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 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
- 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
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 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
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 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 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound 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
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 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 1
- 239000002994 raw material Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Paints Or Removers (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
【発明の詳細な説明】
〔発明の背景〕
〈産業上の利用分野〉
本発明は、導電性、耐環性の優れた銅粉、特に導電塗料
用銅粉を製造するための銅粉の表面処理方法に関する。[Detailed description of the invention] [Background of the invention] Regarding processing method.
〈従来技術〉
従来、銅粉は非常に酸化され易いため種々の表面処理技
術が検討、実施されてきた。<Prior Art> Since copper powder is very easily oxidized, various surface treatment techniques have been studied and implemented.
例えば、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
）、銅粉をカルボン酸処理すること（特開昭６０−２５
８２７３号公報）、銅粉の表面を半田メツキすること（
特開昭５７−１１３５０５号公報）、銅粉の表面に金萬
銀を置換析出させること（特開昭６０−２４３２７７号
公報）などが提案されている。For example, surface treatment of copper powder with a coupling agent (JP-A-60-30200), coating of electrolytic copper powder with an organic titanate (JP-A-59-174661), coating copper powder with a carboxylic acid To process (Unexamined Japanese Patent Publication No. 60-25
No. 8273), soldering the surface of copper powder (
JP-A-57-113505) and substitution precipitation of gold and silver on the surface of copper powder (JP-A-60-243277) have been proposed.
〈発明が解決しようとする課題〉 しかしながら、これらの技術の中には酸化防１１・。<Problem that the invention seeks to solve> However, some of these technologies include antioxidant 11.
を目的としである程度の効果を達成することができるも
のもあるが、銅金属特有の性質である導電性や、耐環性
の点において実用レベルの信頼性が得られるものは存在
しなかった。Although there are some products that can achieve a certain degree of effectiveness, none of them have been able to achieve a practical level of reliability in terms of conductivity and ring resistance, which are properties unique to copper metal.
く要 旨〉
本発明者らは、上記課題に鑑みて鋭意研究を重ねた結果
、特定な溶液で処理した後、特定な化合物で被覆した銅
粉が優れた導電性および耐環性を付与することができる
との知見を得て本発明を完成するに至った。Summary> As a result of extensive research in view of the above issues, the present inventors have discovered that copper powder coated with a specific compound after being treated with a specific solution provides excellent conductivity and ring resistance. The present invention was completed based on the knowledge that this is possible.
すなわち、本発明の銅粉の表面処理方法は、銅粉を金属
アルコキシド溶液で表面処理した後、金属アシレート化
合物で被覆することを特徴とするものである。That is, the method for surface treatment of copper powder of the present invention is characterized in that copper powder is surface treated with a metal alkoxide solution and then coated with a metal acylate compound.
く効 果〉
金属アルコキシド溶液で表面処理した後、金属アシレー
ト化合物で被覆された銅粉は、それに樹脂バインダーを
混合して形成した塗膜が４電性および耐熱性、耐湿性、
樹脂バインダー中における銅粉の分散性などの耐環性が
著しく優れたものであることから導電性塗料として使用
することができる。After surface treatment with a metal alkoxide solution, the copper powder coated with a metal acylate compound has a coating film formed by mixing it with a resin binder, which has four electric properties, heat resistance, moisture resistance,
It can be used as a conductive paint because it has excellent ring resistance such as dispersibility of copper powder in a resin binder.
（Ｉ）銅粉
本発明の銅粉の表面処理方法に用いられる原料としての
銅粉は、電解法、化学還元法、アトマイズ法より得られ
る樹枝状、粒状、針状、球状の形状のもの、あるいは更
に、これらをボールミルなどにより機械的に加工したフ
レーク状のものなどで、これら平均粒径が光透過法で測
定して一般に５０μｍ以下、好ましくは２０μｍ以下の
ものが用いられる。(I) Copper powder Copper powder as a raw material used in the copper powder surface treatment method of the present invention has a dendritic, granular, acicular, or spherical shape obtained by an electrolysis method, a chemical reduction method, or an atomization method; Alternatively, flakes obtained by mechanically processing these with a ball mill or the like, and having an average particle diameter of generally 50 μm or less, preferably 20 μm or less, as measured by a light transmission method, are used.
また、これら樹枝状銅粉、フレーク状銅粉、粒状銅粉、
針状銅粉、および球状銅粉はそれらの二種以上をミキサ
ーやミルなどの混合機を用いて混合して使用することも
できる。In addition, these dendritic copper powder, flaky copper powder, granular copper powder,
Acicular copper powder and spherical copper powder can also be used by mixing two or more of them using a mixer such as a mixer or a mill.
前記銅粉の平均粒径が上記範囲を超えると塗装の均一性
が低下したり、塗膜にザラツキなどが牛じるので、上記
範囲内のものを用いることが好ましい。If the average particle diameter of the copper powder exceeds the above range, the uniformity of the coating may deteriorate and the coating film may become rough, so it is preferable to use one within the above range.
さらに、これら銅粉は、予め、銀、ニッケル、亜鉛、白
金、パラジウムなどの金属、半［１１などの合金、アミ
ン類、アミノ酸、カルボン酸およびその誘導体などの有
機化合物で被覆したものであってもよい。Furthermore, these copper powders are coated in advance with metals such as silver, nickel, zinc, platinum, and palladium, alloys such as semi-[11], and organic compounds such as amines, amino acids, carboxylic acids, and their derivatives. Good too.
使用される銅粉は、必要に応じて、前処理として無機酸
、有機酸、各種還元剤などの試薬を用いたり、水素還元
することにより、銅粉表面からの酸化被覆を除去するこ
とができる。また、被覆されるべき銅粉を予め乾燥する
こともできる。If necessary, the copper powder used can be pretreated with reagents such as inorganic acids, organic acids, various reducing agents, etc., or by hydrogen reduction to remove the oxidized coating from the surface of the copper powder. . It is also possible to dry the copper powder to be coated beforehand.
（ｎ）金属アルコキシドによる表面処理前記銅粉は、本
発明において金属アルコキシド溶液によって表面処理す
ることが重要である。(n) Surface treatment with metal alkoxide In the present invention, it is important to surface treat the copper powder with a metal alkoxide solution.
該金属アルコキシドとしては、一般式
％式％）
（ただし、ＭハＴ ｉ 、 Ｚ ｒ、Ａ Ｉ、Ｐｂｓ
Ｓ ＬＳｎまたはＩｎを表わし、Ｒは炭素数１〜６のア
ルキル基を表わし、ｎは１〜４の整数を表わす。）を使
用することが好ましい。The metal alkoxide has the general formula % (% formula %) (However, M, T i , Z r, A I, Pbs
S LSn or In, R represents an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 4. ) is preferably used.
これら金属アルコキシドの中でも、Ｔｉ、ＺｒまたはＡ
１の金属アルコキシドを用いることか特に好ましい。Among these metal alkoxides, Ti, Zr or A
It is particularly preferable to use the metal alkoxide of No. 1.
具体的には、テトライソプロポキシチタニウム、テトラ
ｎ−ブトキシジルコニウム、テトライソプロポキシジル
コニウム、トリイソプロポキシアルミニウムなどがある
。Specific examples include tetraisopropoxytitanium, tetra-n-butoxyzirconium, tetraisopropoxyzirconium, and triisopropoxyaluminum.
この金属アルコキシドは、その一部が銅粉表面に均一に
効率良く被覆されるようにするために、溶液状態で用い
るのが普通である。溶媒は、水や有機系溶媒、例えばア
ルコール類、エステル類、エーテル類などであり、特別
に限定されるものではない。This metal alkoxide is usually used in a solution state so that a portion of the metal alkoxide can be uniformly and efficiently coated on the surface of the copper powder. The solvent may be water or an organic solvent such as alcohols, esters, ethers, etc., and is not particularly limited.
上記金属アルコキシド化合物で前記銅粉を表面処理する
には、溶媒に溶解した金属アルコキシド化合物に銅粉を
添加し、その後に溶剤を蒸発させて除去する方法、ある
いは銅粉に対し必要量の金属アルコキシド化合物を添加
し、混合攪拌するｈ゛法などがある。To surface-treat the copper powder with the metal alkoxide compound, the copper powder is added to the metal alkoxide compound dissolved in a solvent, and then the solvent is evaporated to remove it, or the necessary amount of metal alkoxide is added to the copper powder. There is a method such as "h" in which a compound is added, mixed and stirred.
表面処理は一般に室温で行なわれる。Surface treatment is generally carried out at room temperature.
この金属アルコキシドは、銅粉重量に対して一般に０．
０００１〜１５重量％、好ましくは０．００１〜１０重
量％の範囲内の量で行なわれ、その一部が表面に被覆さ
れる。これは、０．００１重量％未満では、銅粉の耐環
性が徐々に低下し始めて、０．０００１重量％未満では
、その傾向が著しくなるからである。また１０ｆｆｉｆ
ｆｉ％を超えると、銅粉の導電性が徐々に低下し始めて
、１５重量％を超えると、その傾向が著しくなるからで
ある。This metal alkoxide is generally 0.0% based on the weight of the copper powder.
0.001 to 15% by weight, preferably 0.001 to 10% by weight, a portion of which is coated on the surface. This is because if the content is less than 0.001% by weight, the ring resistance of the copper powder begins to gradually decrease, and if it is less than 0.0001% by weight, this tendency becomes marked. Also 10ffif
This is because when the content exceeds fi%, the conductivity of the copper powder begins to gradually decrease, and when the content exceeds 15% by weight, this tendency becomes remarkable.
このような表面処理によって金属アルコキシドによる金
属酸化物の被膜が形成されて、耐環性、特に耐熱エージ
ング性の向上に作用する。Such a surface treatment forms a metal oxide film of metal alkoxide, which improves ring resistance, particularly heat aging resistance.
Ｃｍ）金属アシレート化合物による被覆上記金属アルコ
キシドによる表面処理の後に、金属アシレート化合物に
よる被覆が行なわれる。Cm) Coating with a metal acylate compound After the surface treatment with the metal alkoxide described above, coating with a metal acylate compound is performed.
このとき用いられる金属アシレート化合物は、Ｔｉもし
くはＺ「のアルコキシドを高級脂肪酸でアシレート化し
たものであることが好ましい。The metal acylate compound used at this time is preferably one obtained by acylating an alkoxide of Ti or Z with a higher fatty acid.
このような金属アシレート化合物としては、例えばテト
ライソプロポキシチタネート、テトラｎ−ブトキシジル
コネートに対して、数倍モルの高級脂肪酸〜カプロン酸
、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン
酸、ステアリン酸、オレイン酸、リノール酸、リルイン
酸、リシノール酸及びその異性体などを反応させて得ら
れるものである。Such metal acylate compounds include, for example, tetraisopropoxy titanate, tetra-n-butoxyzirconate, and several times the molar amount of higher fatty acids to caproic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, It is obtained by reacting oleic acid, linoleic acid, liluic acid, ricinoleic acid, and isomers thereof.
上記金属アシレート化合物を前記銅粉に被覆するには、
溶媒に溶解した金属アシレート化合物に銅粉を添加し、
その後に溶剤を蒸発させて除去する方法、あるいは銅粉
に対し必要量の金属アシレート化合物を添加し、混合攪
拌する方法などがある。To coat the copper powder with the metal acylate compound,
Copper powder is added to a metal acylate compound dissolved in a solvent,
There is a method in which the solvent is then removed by evaporation, or a method in which a required amount of metal acylate compound is added to the copper powder and mixed and stirred.
被覆処理は一般に室温で行なわれる。The coating process is generally carried out at room temperature.
この金属アシレート化合物は、銅粉重量に対して０．０
００１〜１５重量％、好ましくは０．００１〜１０重量
％の範囲内で波頂される。This metal acylate compound is 0.0% based on the weight of copper powder.
0.001 to 15% by weight, preferably 0.001 to 10% by weight.
これは、０．００１重量％未満では、銅粉の耐環性が徐
々に低下し始めるとともに、樹脂バインダー中における
銅粉の分散性も徐々に低下し始めて、０．０００１重量
％未満ではその傾向が著しくなる。また、１０重量％を
超えると、銅粉の導電性が徐々に低下し始めて、１５重
量％を超えると、その傾向が著しくなる。This is because when the amount is less than 0.001% by weight, the ring resistance of the copper powder starts to gradually decrease, and the dispersibility of the copper powder in the resin binder also starts to gradually decrease. becomes significant. Moreover, when the content exceeds 10% by weight, the conductivity of the copper powder begins to gradually decrease, and when the content exceeds 15% by weight, this tendency becomes remarkable.
この金属アシレート化合物は、湿式、すなわち溶液中に
おいて処理されたり、乾式、すなわち非液中において処
理されたり、銅粉表面に対する被覆方法を特別に限定す
るものではない。The metal acylate compound may be treated wet, ie, in a solution, or dry, ie, in a non-liquid, and the method of coating the surface of the copper powder is not particularly limited.
このようにして形成された金属アシレート化合物の被覆
は、耐環性、特に耐湿エージング性の向上と樹脂バイン
ダー中における分散性の向上に寄与して、結果的に導電
性を向上させることができる。The metal acylate compound coating thus formed contributes to improved ring resistance, particularly moisture aging resistance, and improved dispersibility in the resin binder, resulting in improved electrical conductivity.
（ＴＶ）導電性塗料用銅粉
このようにして製造された導電性塗料用銅粉は、比較的
低価格の被覆材料で、銀被覆に匹敵する導電性および耐
環性を有している。(TV) Copper Powder for Conductive Paint The copper powder for conductive paint produced in this way is a relatively low-cost coating material and has electrical conductivity and ring resistance comparable to silver coating.
（Ｖ）用途／導電性塗料組成物
このような導電性塗料用銅粉に、樹脂バインダーと、溶
剤とを含有させることによって導電性塗料用組成物が得
られる。(V) Application/Conductive paint composition A composition for conductive paint can be obtained by incorporating a resin binder and a solvent into such copper powder for conductive paint.
該導電性塗料用組成物中に配合される導電性塗料用銅粉
の量は、溶剤分を除く組成物中で、一般に４０〜９５重
量％であり、好ましくは５０〜９０重量％である。これ
は、５０重量％未満では組成物中の銅粉含有率の低下に
伴い組成物の導電性が徐々に低下し始め、４０重量９６
未満では、その傾向が著しくなるからである。また、９
０重量％を超えると組成物中の銅粉含有率が過剰になり
、導電性および基材に対する密着性ｔどの物理的強度が
低下し始め、９５重量％を超えるとその傾向が著しくな
るからである。The amount of copper powder for conductive paint blended into the composition for conductive paint is generally 40 to 95% by weight, preferably 50 to 90% by weight, based on the composition excluding the solvent. This means that if it is less than 50% by weight, the conductivity of the composition will gradually decrease as the content of copper powder in the composition decreases.
This is because, if it is less than that, this tendency becomes more pronounced. Also, 9
If it exceeds 0% by weight, the copper powder content in the composition becomes excessive, and physical strength such as conductivity and adhesion to the substrate begins to decrease, and if it exceeds 95% by weight, this tendency becomes remarkable. be.
前記樹脂バインダーとしては、一般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もの
である。具体的には、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
では、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
キシ系樹脂などを挙げることができる。The resin binder is one that has good adhesion to plastics commonly used in electronic devices. Specifically, ABS, polystyrene, PPO,
Examples of plastics for electronic device housings such as polycarbonate include acrylic resins, polyurethane resins, polyester resins, styrene resins, phenolic resins, and epoxy resins.
また、この導電性塗料用組成物に配合される樹脂バイン
ダーの量としては、組成物の固形分に対して、一般に５
〜６０重量％であり、好ましくは、１０〜５０重量％で
ある。In addition, the amount of the resin binder added to this conductive coating composition is generally 5% based on the solid content of the composition.
-60% by weight, preferably 10-50% by weight.
前記溶剤としては、前記樹脂バインダーなどを溶解する
トルエン、ヘキサン、ベンゼン、メチルエチルケトン、
キシレン、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、メチルイソブチル
ケトン、酢酸エチル、酢酸ブチル、メチルセロソルブ、
エチルセロソルブなどの有機溶剤の１種または２種以上
の混合物を用いることが好ましい。Examples of the solvent include toluene, hexane, benzene, methyl ethyl ketone, which dissolves the resin binder, etc.
xylene, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, methyl isobutyl ketone, ethyl acetate, butyl acetate, methyl cellosolve,
It is preferable to use one or a mixture of two or more organic solvents such as ethyl cellosolve.
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７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、難燃剤などがある。In addition to the above components, various additives can be included depending on the purpose. Such substances 7 include reducing agents, surfactants, antisettling agents, antifoaming agents, thickeners, thixotropic agents, rust preventives, flame retardants, and the like.
（Ｖｌ）実験例 本発明を、以下の実験例によって具体的に説明する。(Vl) Experimental example The present invention will be specifically explained using the following experimental examples.
実験材料 実験例において用いた材料を以下に示す。experimental materials The materials used in the experimental examples are shown below.
く銅 粉〉
樹枝状電解銅粉：三井金属鉱業（株）ＭＦ−Ｄ２の性状
は第１表に示すとおりである。Properties of dendritic electrolytic copper powder: MF-D2 manufactured by Mitsui Mining & Smelting Co., Ltd. are shown in Table 1.
く金属アルコキシド〉
く金属アシレート化合物〉
第２表
第 ３
表
〈比較サンプル〉
第４表
実施例１
酸化被膜の除去された第１表の銅粉にχｌて、第２表の
金属アルコキシド（Ｎｏ、２−１〜２−７）を室温で銅
粉に対し必要量添加し、Ｖ型ミキサーで混合攪拌する方
法によって表面処理した後、第３表の金属アシレート化
合物（Ｎｏ、３−１〜３−１０）を室温で銅粉に対し必
要量添加し、■型ミキサーで混合攪拌する方法で被覆処
理を行ない、各々銅粉重量に対して０． ５．１．０．
３． Ｏ１５，０，１０，０重量％で被覆した。Metal alkoxide〉 Metal acylate compound〉 Table 2 Table 3 <Comparative sample> Table 4 Example 1 The metal alkoxides (No. 2-1 to 2-7) to copper powder at room temperature, and after surface treatment by mixing and stirring with a V-type mixer, metal acylate compounds (No. 3-1 to 3-3) in Table 3 were added. 10) was added in the required amount to the copper powder at room temperature, and the coating treatment was carried out by mixing and stirring with a type 2 mixer. 5.1.0.
3. Coated with O15.0, 10.0% by weight.
これら被覆処理された銅粉をアクリル系樹脂（固型分＝
６０重量％）とトルエンを用いて導電性塗料を調整して
体積固有抵抗を測定した。These coated copper powders are coated with acrylic resin (solid content =
60% by weight) and toluene to prepare a conductive paint and measure its volume resistivity.
その結果、導電性塗料は体積固有抵抗がおよそ２×１０
〜４Ｘ１０’Ω・０であった。As a result, the conductive paint has a volume resistivity of approximately 2×10
It was ~4×10′Ω・0.
４
また、この塗膜基板（アクリル板〜厚さ１，５ｍｍ、導
体サイズ２ＣＩＩＸ２ＣＩＩ）を８５℃の高温、６０℃
／９５％ＲＨの高湿度環境に２０００時間放置して塗膜
を観察した。4 In addition, this coated substrate (acrylic board ~ thickness 1.5 mm, conductor size 2CIIX2CII) was heated at a high temperature of 85℃ and 60℃.
The coating film was observed after being left in a high humidity environment of /95% RH for 2000 hours.
その結果、本発明の導電性塗料は、８５℃の高温、６０
℃／９５％ＲＨの湿度環境下における緑青の発生率は少
なくて１％、多くても７％程度で、はとんどが３〜４％
であった。また６０℃／９５％ＲＨの高湿における緑青
の発生率は０．７％で、はとんどが０％であった。As a result, the conductive paint of the present invention can be used at high temperatures of 85°C and 60°C.
The incidence of patina in a humidity environment of ℃/95% RH is at least 1%, at most 7%, and most is 3-4%.
Met. Furthermore, the incidence of patina at high humidity of 60° C./95% RH was 0.7%, mostly 0%.
以上の結果より、本発明の銅粉の表面処理方法で被覆処
理された銅粉より調整された導電性塗料は、優れた導電
性および耐湿エージング特性をＨしていることがわかっ
た。From the above results, it was found that the conductive paint prepared from the copper powder coated by the copper powder surface treatment method of the present invention has excellent conductivity and moisture aging resistance.
比較例１〜３
第２表の金属アルコキシドの表面処理のみを（比較例１
）、また第３表の金属アシレート化合物による被覆のみ
を（比較例２）、更に、金属アルコキシドおよび金属ア
シレート化合物の処理を行なわず第４表の有機化合物を
銅粉重量に対して０．００１．０，０５．０． １．１
，０．３．０．６．０．１０． ０ｆｆｉ量％の量で用
いて処理を（比較例３）行なった以外は実施例１と同様
にして行ない、導電性塗料を得た。Comparative Examples 1 to 3 Only the surface treatment of the metal alkoxide in Table 2 (Comparative Example 1
), coating only with the metal acylate compound shown in Table 3 (Comparative Example 2), and coating with the organic compound shown in Table 4 without treatment with metal alkoxide or metal acylate compound at a coating rate of 0.001. 0,05.0. 1.1
,0.3.0.6.0.10. A conductive paint was obtained in the same manner as in Example 1, except that the treatment was carried out using 0ffi% (Comparative Example 3).
この導電性塗料を実施例１と同様に体積内６°抵抗を測
定した結果、比較ｆｌｌ １は９Ｘ１０−’〜３×３
１０ Ω・国であり、比較例２は３〜５Ｘ１（１−４Ω
・備であり、比較例３は９Ｘ１０−４〜３×１０−３Ω
・国であった。As a result of measuring the internal 6° resistance of this conductive paint in the same manner as in Example 1, Comparative example 1 had a resistance of 9X10-' to 3x310 Ω, and Comparative example 2 had a resistance of 3 to 5X1 (1-4Ω
・Comparative example 3 has a resistance of 9×10-4 to 3×10-3Ω
・It was a country.
また、この導電性塗料より形成した塗膜を失施例１と同
様にして高湿度環境下での測定を行なった。Further, a coating film formed from this conductive paint was subjected to measurements in a high humidity environment in the same manner as in Example 1.
比較例１〜３による導電性塗料の塗膜基板は、８５℃の
高温における緑青の発生率は、３０〜１１５％であった
。また６０℃／９５％ＲＨの高湿における緑青の発生率
は２４〜８４％であった。The coating substrates of the conductive paints according to Comparative Examples 1 to 3 had a patina generation rate of 30 to 115% at a high temperature of 85°C. Moreover, the occurrence rate of patina at high humidity of 60° C./95% RH was 24 to 84%.
Claims (3)
属アシレート化合物で被覆することを特徴とする銅粉の
表面処理方法。1. A method for surface treatment of copper powder, characterized in that the surface of copper powder is treated with a metal alkoxide solution and then coated with a metal acylate compound.
たはＩｎを表わし、Ｒは炭素数１〜６のアルキル基を表
わし、ｎは１〜４の整数を表わす。）で表わされるもの
である請求項１に記載の銅粉の表面処理方法。2. Metal alkoxide has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, M represents Ti, Zr, Al, Pb, Si, Sn or In, R represents an alkyl group having 1 to 6 carbon atoms, The method for surface treatment of copper powder according to claim 1, wherein n represents an integer from 1 to 4.
コキシドを高級脂肪酸でアシレート化して得られたもの
である請求項１または２に記載の銅粉の表面処理方法。3. 3. The method for surface treatment of copper powder according to claim 1, wherein the metal acylate compound is obtained by acylating Ti or Zr alkoxide with a higher fatty acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1205344A JPH0368702A (en) | 1989-08-08 | 1989-08-08 | Method for treating surface of copper powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1205344A JPH0368702A (en) | 1989-08-08 | 1989-08-08 | Method for treating surface of copper powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0368702A true JPH0368702A (en) | 1991-03-25 |
Family
ID=16505337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1205344A Pending JPH0368702A (en) | 1989-08-08 | 1989-08-08 | Method for treating surface of copper powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0368702A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047417A1 (en) * | 1996-06-10 | 1997-12-18 | Nittetsu Mining Co., Ltd. | Powder coated with multilayer film and process for preparing the same |
| WO2002087809A1 (en) * | 2001-04-27 | 2002-11-07 | Dowa Mining Co., Ltd. | Copper powder for electroconductive paste excellent in resistance to oxidation and method for preparation thereof |
-
1989
- 1989-08-08 JP JP1205344A patent/JPH0368702A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997047417A1 (en) * | 1996-06-10 | 1997-12-18 | Nittetsu Mining Co., Ltd. | Powder coated with multilayer film and process for preparing the same |
| WO2002087809A1 (en) * | 2001-04-27 | 2002-11-07 | Dowa Mining Co., Ltd. | Copper powder for electroconductive paste excellent in resistance to oxidation and method for preparation thereof |
| US7393586B2 (en) | 2001-04-27 | 2008-07-01 | Dowa Electronics Materials Co., Ltd. | Highly oxidation-resistant copper powder for conductive paste and process for producing the powder |
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