JP4164008B2 - 銅粉末及びその製造方法並びにそれを用いた銅ペースト・塗料、電極 - Google Patents
銅粉末及びその製造方法並びにそれを用いた銅ペースト・塗料、電極 Download PDFInfo
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- JP4164008B2 JP4164008B2 JP2003292861A JP2003292861A JP4164008B2 JP 4164008 B2 JP4164008 B2 JP 4164008B2 JP 2003292861 A JP2003292861 A JP 2003292861A JP 2003292861 A JP2003292861 A JP 2003292861A JP 4164008 B2 JP4164008 B2 JP 4164008B2
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- Prior art keywords
- copper
- particles
- weight
- copper powder
- polysiloxane
- 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.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 126
- 229910052802 copper Inorganic materials 0.000 title claims description 84
- 239000010949 copper Substances 0.000 title claims description 84
- 239000003973 paint Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims description 64
- -1 polysiloxane Polymers 0.000 claims description 62
- 229920001296 polysiloxane Polymers 0.000 claims description 40
- 229920002545 silicone oil Polymers 0.000 claims description 31
- 239000005749 Copper compound Substances 0.000 claims description 16
- 150000001880 copper compounds Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 34
- 230000003647 oxidation Effects 0.000 description 18
- 238000007254 oxidation reaction Methods 0.000 description 18
- 125000000524 functional group Chemical group 0.000 description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
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- 239000005751 Copper oxide Substances 0.000 description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
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- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 6
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 4
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- 239000001307 helium Substances 0.000 description 4
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- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 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
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229940080237 sodium caseinate Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HLJWMCUZPYEUDI-UHFFFAOYSA-L sodium hyponitrite Chemical compound [Na+].[Na+].[O-]N=N[O-] HLJWMCUZPYEUDI-UHFFFAOYSA-L 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- GWBUNZLLLLDXMD-UHFFFAOYSA-H tricopper;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[O-]C([O-])=O.[O-]C([O-])=O GWBUNZLLLLDXMD-UHFFFAOYSA-H 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
Description
(化1)
CH3 CH3 CH3 CH3 CH3
│ │ │ │ │
式(1):X1―SiO(SiO)n(SiO)m(SiO)lSi―X2
│ │ │ │ │
CH3 X3 X4 X5 CH3
[式(1)中、X1〜5がメチル基または官能基で、nは1以上の整数でm、lはそれぞれ0または1以上の整数であり、X1〜5の少なくとも2個が官能基の場合、官能基は同種であっても異種であっても良い。]
工業用亜酸化銅(NC−102:エヌシーテック社製)30g、硫黄化合物として3−メルカプトプロピオン酸0.085g、保護コロイドとしてゼラチン5gを400ミリリットルの純水に添加、混合し、10%の硫酸を用いて混合液のpHを7に調整した後、20分かけて室温から90℃まで昇温した。昇温後、撹拌しながら80%ヒドラジン一水和物を添加し、2時間かけて亜酸化銅と反応させ、銅粒子に対し3−メルカプトプロピオン酸を1.3重量%処理した平均粒子径が0.45μmの銅微粒子を生成させた。その後、濾液比抵抗が100μS/cm以下になるまで濾過洗浄し、窒素ガスの雰囲気下で60℃の温度で10時間かけて乾燥し、銅粒子を得た。次いで、銅粒子とこれに対し8重量%に相当するメチルハイドロジェンポリシロキサン(SH−1107:前式(1)のm、lが0でありX3が水素基、X1、X2がメチル基のもの、東レダウコーニングシリコーン社製)とを、ブレンダーを用いて5分間撹拌して乾式処理した後、窒素ガスの雰囲気下で120℃の温度で2時間加熱処理して本発明の銅粉末(試料A)を得た。
メチルハイドロジェンポリシロキサンの処理量を10重量%に変更したこと以外は実施例1と同様にして本発明の銅粉末(試料B)を得た。
メチルハイドロジェンポリシロキサンをジメチルポリシロキサン(SH−200:前式(1)のm、lが0でありX1〜X3がメチル基のもの、東レダウコーニングシリコーン社製)に替えたこと以外は実施例1、2と同様にして本発明の銅粉末(それぞれ実施例3−試料C、実施例4−試料D)を得た。また、加熱処理温度を300℃に変更したこと以外は実施例4と同様にして本発明の銅粉末(実施例5−試料E)を得た。
メチルハイドロジェンポリシロキサンをメチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体(KF−9901:信越化学工業社製)に替えたこと以外は実施例2と同様にして本発明の銅粉末(試料F)を得た。
メチルハイドロジェンポリシロキサンをメルカプト変性ポリシロキサン(KF−2004:前式(1)のlが0でありX1〜3がメチル基でX4がメルカプト基のもの、信越化学工業社製)に替えたこと以外は実施例1と同様にして本発明の銅粉末(試料G)を得た。
実施例1と同様にして銅粒子を得た後、銅粒子を2−プロパノール中に分散させ、500g/リットルのスラリーとし、銅粒子に対して4重量%に相当するメルカプト変性ポリシロキサン(KF−2004:信越化学工業社製)をこのスラリーに添加して30分間撹拌して湿式処理した。その後、蒸発乾固により、銅粒子を固液分離した。次いで、銅粒子を窒素ガスの雰囲気下で120℃の温度で5時間加熱処理した後、乳鉢で粉砕し本発明の銅粉末(試料H)を得た。
保護コロイドとしてアラビアゴム2gを2900ミリリットルの純水に添加した後、工業用酸化銅(N−120:エヌシーテック社製)125gを添加し撹拌しながら、80%ヒドラジン一水和物を360ミリリットル添加した。ヒドラジン一水和物の添加後から3時間かけ室温から60℃に昇温し、更に2時間かけて酸化銅と反応させ、平均粒子径が0.6μmの銅粒子を生成させた。その後、濾液比抵抗が100μS/cm以下になるまで濾過洗浄し、窒素ガスの雰囲気下で60℃の温度で10時間かけて乾燥し、銅粒子を得た。次いで、実施例1と同様にしてメチルハイドロジェンポリシロキサン(SH−1107)を乾式処理した後、加熱処理して銅粉末(試料I)を得た。また、シリコーンオイルをジメチルポリシロキサン(SH−200)に替えたこと以外は比較例1と同様にして、銅粉末を(比較例2−試料J)得た。
比較例1及び実施例1において、メチルハイドロジェンポリシロキサンを処理せず、また加熱処理せずに得た銅粉末を、それぞれ比較例3、4(試料K、L)とする。また、比較例4において、300℃の温度で2時間加熱処理したこと以外は同様にして得た銅粉末を比較例5(試料M)とする。
実施例1〜8、比較例1〜5で得られた試料A〜M10gを、非酸化性窒素ガス雰囲気下60℃の温度で10時間加熱した後の金属銅重量と、その後更に、酸化性空気雰囲気下150℃、200℃、300℃、400℃、500℃の温度で、それぞれ20分間加熱焼成した後の重量を測定し、重量増加率を算出した。結果を表1に示す。重量増加が少ない程、耐酸化性が優れていることを示しており、本発明の銅粉末は重量増加率が低く、耐酸化性が優れていることが判る。特に、本発明の銅粉末は、500℃の温度で加熱焼成した後の重量増加率が15%以下であり、良好であった。
Claims (6)
- ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体、メルカプト変性ポリシロキサンから選ばれる少なくとも1種のシリコーンオイルとメルカプトプロピオン酸とが銅粒子の表面に結合および/または吸着していることを特徴とする銅粉末。
- 非酸化性雰囲気下60℃の温度で10時間加熱後の重量(W1)に対し、更に酸化性雰囲気下500℃の温度で20分間加熱後の重量(W2)の増加率((W2−W1)/W1×100)が最大で15%であることを特徴とする請求項1記載の銅粉末。
- 銅粒子に対しシリコーンオイルの処理量が0.2〜20重量%の範囲で、メルカプトプロピオン酸の処理量が0.1〜20重量%の範囲であることを特徴とする請求項1記載の銅粉末。
- メルカプトプロピオン酸及び保護コロイドの存在下で銅化合物と還元剤とを反応させてメルカプトプロピオン酸が結合および/または吸着した銅粒子を得る工程、得られた銅粒子に、ジメチルポリシロキサン、メチルハイドロジェンポリシロキサン、メチルハイドロジェンポリシロキサン・ジメチルポリシロキサン共重合体、メルカプト変性ポリシロキサンから選ばれる少なくとも1種のシリコーンオイルを表面処理させる工程とからなることを特徴とするシリコーンオイルとメルカプトプロピオン酸とが銅粒子の表面に結合および/または吸着した銅粉末の製造方法。
- 請求項1記載の銅粉末を配合してなる銅ペーストまたは銅塗料。
- 請求項1記載の銅粉末を用いた電極。
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