JP4628701B2 - Copper and copper alloy surface treatment agent, aqueous solution thereof, surface-treated copper and copper alloy, and surface treatment method of copper and copper alloy - Google Patents
Copper and copper alloy surface treatment agent, aqueous solution thereof, surface-treated copper and copper alloy, and surface treatment method of copper and copper alloy Download PDFInfo
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- JP4628701B2 JP4628701B2 JP2004177213A JP2004177213A JP4628701B2 JP 4628701 B2 JP4628701 B2 JP 4628701B2 JP 2004177213 A JP2004177213 A JP 2004177213A JP 2004177213 A JP2004177213 A JP 2004177213A JP 4628701 B2 JP4628701 B2 JP 4628701B2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 65
- 239000010949 copper Substances 0.000 title claims description 65
- 229910052802 copper Inorganic materials 0.000 title claims description 63
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 56
- 239000012756 surface treatment agent Substances 0.000 title claims description 24
- 239000007864 aqueous solution Substances 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 11
- 238000004381 surface treatment Methods 0.000 title claims description 9
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 15
- -1 triazole compound Chemical class 0.000 claims description 15
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- 235000011044 succinic acid Nutrition 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 238000004649 discoloration prevention Methods 0.000 description 12
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000002845 discoloration Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910001369 Brass Inorganic materials 0.000 description 4
- 229910000906 Bronze Inorganic materials 0.000 description 4
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- 239000010951 brass Substances 0.000 description 4
- 239000010974 bronze Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
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- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
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- KFJDQPJLANOOOB-UHFFFAOYSA-N 2h-benzotriazole-4-carboxylic acid Chemical compound OC(=O)C1=CC=CC2=NNN=C12 KFJDQPJLANOOOB-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
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- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- MZQZXSHFWDHNOW-UHFFFAOYSA-N 1-phenylpropane-1,2-diol Chemical compound CC(O)C(O)C1=CC=CC=C1 MZQZXSHFWDHNOW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
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- DXPLEDYRQHTBDJ-CCEZHUSRSA-N 2-[(E)-pentadec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O DXPLEDYRQHTBDJ-CCEZHUSRSA-N 0.000 description 1
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 description 1
- DMNJWIGKABXQGQ-AATRIKPKSA-N 2-[(e)-hex-1-enyl]butanedioic acid Chemical compound CCCC\C=C\C(C(O)=O)CC(O)=O DMNJWIGKABXQGQ-AATRIKPKSA-N 0.000 description 1
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- ZPJDFKVKOFGAFV-UHFFFAOYSA-N 2-octadecylbutanedioic acid Chemical compound CCCCCCCCCCCCCCCCCCC(C(O)=O)CC(O)=O ZPJDFKVKOFGAFV-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- DBKSSENEKWOVKL-UHFFFAOYSA-N 4-(methylamino)butan-1-ol Chemical compound CNCCCCO DBKSSENEKWOVKL-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- QRHDSDJIMDCCKE-UHFFFAOYSA-N 4-ethyl-2h-benzotriazole Chemical compound CCC1=CC=CC2=C1N=NN2 QRHDSDJIMDCCKE-UHFFFAOYSA-N 0.000 description 1
- 102100032373 Coiled-coil domain-containing protein 85B Human genes 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AAHZZGHPCKJNNZ-UHFFFAOYSA-N Hexadecenylsuccinicacid Chemical compound CCCCCCCCCCCCCCC=CC(C(O)=O)CC(O)=O AAHZZGHPCKJNNZ-UHFFFAOYSA-N 0.000 description 1
- 101000868814 Homo sapiens Coiled-coil domain-containing protein 85B Proteins 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- KCYQMQGPYWZZNJ-BQYQJAHWSA-N hydron;2-[(e)-oct-1-enyl]butanedioate Chemical compound CCCCCC\C=C\C(C(O)=O)CC(O)=O KCYQMQGPYWZZNJ-BQYQJAHWSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SCZVXVGZMZRGRU-UHFFFAOYSA-N n'-ethylethane-1,2-diamine Chemical compound CCNCCN SCZVXVGZMZRGRU-UHFFFAOYSA-N 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、銅で形成される電気部品や銅で回路を形成されるプリント配線板、その他銅のメッキを表面に形成した部品等において、銅の腐食変色を防止する水溶性の銅及び銅合金用表面処理剤に関するものである。 The present invention relates to water-soluble copper and copper alloys for preventing corrosion discoloration of copper in electrical parts formed of copper, printed wiring boards formed of circuits of copper, and other parts formed with copper plating on the surface. The present invention relates to a surface treatment agent.
従来から、銅又は銅合金で形成される電気部品や銅又は銅合金で回路を形成されるプリント配線板、その他銅のメッキを表面に形成した部品等において、銅及び銅合金の表面は用意に腐食されて変色されるために、変色防止剤での処理により、腐食変色を防止することが行われている。この銅及び銅合金の変色防止剤としては、ベンゾトリアゾール等を含む溶液が用いられている（例えば、下記特許文献１）。
しかし、従来のものは、結露が発生するような厳しい腐食環境では、変色防止作用が不十分なために、銅及び銅合金の変色が発生する場合がある。また、変色防止剤が乾燥することで、その残渣が銅及び銅合金の表面に残ることもあり、美観の点や絞りロール等に付着する等の後工程等において問題となることがあった。 However, the conventional one may cause discoloration of copper and copper alloy in a severe corrosive environment where dew condensation occurs because the discoloration preventing action is insufficient. In addition, drying of the anti-discoloring agent may leave the residue on the surface of copper and copper alloy, which may cause problems in post-processes such as adhering to aesthetic points and squeezing rolls.
そこで、本発明の目的は、結露が発生するような厳しい腐食環境でも、銅及び銅合金の変色防止が十分にでき、かつ、乾燥しても残渣が残らない水溶性銅用表面処理剤、その水溶液、この水溶液によって表面処理された銅及び銅合金、及び銅及び銅合金の表面処理方法を提供することである。 Therefore, an object of the present invention is to provide a water-soluble surface treatment agent for water-soluble copper that can sufficiently prevent discoloration of copper and copper alloy even in a severe corrosive environment in which condensation occurs, and that no residue remains even when dried. To provide an aqueous solution, copper and a copper alloy surface-treated with the aqueous solution, and a surface treatment method for copper and a copper alloy.
本発明に係る水溶性の銅及び銅合金用表面処理剤は、大気と接触する表面皮膜を形成する銅及び銅合金用表面処理剤であって、１種以上のトリアゾール系化合物と、１種以上のアミン類と、下記一般式〔Ｉ〕で示されるアルケニルコハク酸群の中から選ばれる１種以上のアルケニルコハク酸とを含有するものである。
(化２) ＣＨ２ＣＯＯＨ
｜
Ｒ−ＣＨ−ＣＯＯＨ ・・・・・〔Ｉ〕
（式中、Ｒは炭素原子数６〜３０のアルケニル基を表す。）
また、本発明に係る水溶性の銅及び銅合金用表面処理剤は、１種以上のグリコール類をさらに含有することが好ましい。また、前記１種以上のトリアゾール系化合物の濃度が１ｐｐｍ以上であることが好ましく、また、５０００ｐｐｍ未満であることが好ましいが、さらに１００〜４００ｐｐｍであることが好ましい。また、前記１種以上のアルケニルコハク酸の濃度が５ｐｐｍ以上であることが好ましく、また、５０００ｐｐｍ未満であることが好ましいが、さらに１００〜４００ｐｐｍであることが好ましい。
The water-soluble surface treatment agent for copper and copper alloy according to the present invention is a surface treatment agent for copper and copper alloy that forms a surface film that comes into contact with the atmosphere, and includes one or more triazole compounds and one or more types. And one or more alkenyl succinic acids selected from the alkenyl succinic acid group represented by the following general formula [I].
(Chemical Formula 2) CH 2 COOH
｜
R-CH-COOH [I]
(In the formula, R represents an alkenyl group having 6 to 30 carbon atoms.)
The water-soluble surface treatment agent for copper and copper alloy according to the present invention preferably further contains one or more glycols. Further, the concentration of the one or more triazole compounds is preferably 1 ppm or more, and preferably less than 5000 ppm, and more preferably 100 to 400 ppm. Further, the concentration of the one or more alkenyl succinic acids is preferably 5 ppm or more, and preferably less than 5000 ppm, and more preferably 100 to 400 ppm.
また、上記の銅及び銅合金用表面処理剤を用いる場合には、水溶液として用いることが好ましい。また、本発明の銅又は銅合金は、上記の銅及び銅合金用表面処理剤の水溶液により表面処理されたものであることが好ましい。また、本発明の銅又は銅合金の表面処理方法は、上記の水溶液を銅又は銅合金の表面に塗布又は散布し、若しくは、上記の水溶液に銅又は銅合金を浸漬することによって、銅又は銅合金の表面の処理を行うことが好ましい。 Moreover, when using said copper and the surface treatment agent for copper alloys, it is preferable to use as aqueous solution. Moreover, it is preferable that the copper or copper alloy of this invention is surface-treated with the aqueous solution of the surface treating agent for copper and copper alloy. Moreover, the surface treatment method for copper or copper alloy of the present invention can be obtained by applying or spraying the above aqueous solution on the surface of copper or copper alloy, or by immersing copper or copper alloy in the above aqueous solution. It is preferable to treat the surface of the alloy.
上記構成により、銅及び銅合金の変色防止性能を従来よりも格段に高めることができ、しかも使用後の乾燥残渣のない水溶性の銅及び銅合金用表面処理剤を提供できる。
また、本発明の銅及び銅合金用表面処理剤の水溶液及び表面処理方法を用いることによって、高い変色防止性能を有する銅及び銅合金を得ることができる。
By the said structure, the discoloration prevention performance of copper and a copper alloy can be improved markedly conventionally, and also the water-soluble surface treatment agent for copper and copper alloys without the dry residue after use can be provided.
Moreover, the copper and copper alloy which have high discoloration prevention performance can be obtained by using the aqueous solution and surface treatment method of the surface treating agent for copper and copper alloy of this invention.
以下、本発明に係る実施の形態について説明する。
本発明の実施の形態に係る銅及び銅合金用表面処理剤は、大気と接触する表面皮膜を形成する銅及び銅合金用表面処理剤であって、１種以上のトリアゾール系化合物と、１種以上のアミン類と、下記一般式〔Ｉ〕で示されるアルケニルコハク酸群の中から選ばれる１種以上のアルケニルコハク酸とを含有するものである。
(化３) ＣＨ２ＣＯＯＨ
｜
Ｒ−ＣＨ−ＣＯＯＨ ・・・・・〔Ｉ〕
（式中、Ｒは炭素原子数６〜３０のアルケニル基を表す。）
また、本発明の実施の形態に係る銅及び銅合金用表面処理剤は、１種以上のグリコール類をさらに含有することが好ましい。
Embodiments according to the present invention will be described below.
The surface treatment agent for copper and copper alloy according to the embodiment of the present invention is a surface treatment agent for copper and copper alloy that forms a surface film that comes into contact with the atmosphere, and includes one or more triazole compounds and one type It contains the above amines and one or more alkenyl succinic acids selected from the alkenyl succinic acid group represented by the following general formula [I].
(Chemical Formula 3) CH 2 COOH
｜
R-CH-COOH [I]
(In the formula, R represents an alkenyl group having 6 to 30 carbon atoms.)
Moreover, it is preferable that the surface treatment agent for copper and copper alloy which concerns on embodiment of this invention further contains 1 or more types of glycols.
ここで、トリアゾール系化合物としては、ベンゾトリアゾール、トリルトリアゾール、カルボキシベンゾトリアゾール、クロロベンゾトリアゾール、エチルベンゾトリアゾール、ナフトトリアゾール等が挙げられる。なお、トリアゾール系化合物の濃度は５ｐｐｍ以上であることが好ましく、また、５０００ｐｐｍ未満であることが好ましいが、さらに１００〜４００ｐｐｍであることが好ましい。濃度が５０００ｐｐｍ以上であると、変色防止効果が飽和して不経済となるためで、１００〜４００ｐｐｍであることが好ましいのは、防錆効果を得るのに最適な濃度だからである。 Here, examples of the triazole compound include benzotriazole, tolyltriazole, carboxybenzotriazole, chlorobenzotriazole, ethylbenzotriazole, and naphthotriazole. In addition, it is preferable that the density | concentration of a triazole type compound is 5 ppm or more, and it is preferable that it is less than 5000 ppm, but it is still more preferable that it is 100-400 ppm. If the concentration is 5000 ppm or more, the discoloration prevention effect is saturated and uneconomical, and the concentration of 100 to 400 ppm is preferable because it is the optimum concentration for obtaining the rust prevention effect.
また、上記式〔Ｉ〕で示されるアルケニルコハク酸群としては、具体的には、へキセニルコハク酸、オクテニルコハク酸、デセニルコハク酸、ドデセニルコハク酸、ペンタデセニルコハク酸、ヘキサデセニルコハク酸、オクタデセニルコハク酸、エイコセニルコハク酸等の群が挙げられる。なお、１種以上からなるアルケニルコハク酸の濃度は５ｐｐｍ以上であることが好ましく、また、５０００ｐｐｍ未満であることが好ましいが、さらに１００〜４００ｐｐｍであることが好ましい。濃度が５０００ｐｐｍ以上であると、変色防止効果が飽和して不経済となるためで、１００〜４００ｐｐｍであることが好ましいのは、防錆効果を得るのに最適な濃度だからである。 Specific examples of the alkenyl succinic acid group represented by the formula [I] include hexenyl succinic acid, octenyl succinic acid, decenyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, hexadecenyl succinic acid, octadecyl succinic acid, Examples include groups such as decenyl succinic acid and eicosenyl succinic acid. In addition, the concentration of one or more alkenyl succinic acids is preferably 5 ppm or more, and preferably less than 5000 ppm, and more preferably 100 to 400 ppm. If the concentration is 5000 ppm or more, the discoloration prevention effect is saturated and uneconomical, and the concentration of 100 to 400 ppm is preferable because it is the optimum concentration for obtaining the rust prevention effect.
また、アミン類としては、アンモニア、エチレンジアミン、トリエチレンテトラミン、ジイソプロパノールアミン、トリエタノールアミン、モノエタノールアミン、ジエタノールアミン、モノイソプロパノールアミン、トリイソプロパノールアミン、ジエチレントリアミン、ジエチルアミン、ジブチルアミン、ヘキサヒドロアニリン、ペンタエチレンヘキサミン、アリルアミン、２−アミノプロパノール、３−アミノプロパノール、４−アミノブタノール、４−メチルアミノブタノール、エチルアミノエチルアミン等が挙げられる。
グリコール類としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、メチルジグリコール、アリルグリコール、イソブチルグリコール、ブチルジグリコール、イソブチルジグリコール、メチルトリグリコール、ブチルトリグリコール、グリセリン、ブチルプロピレングリコール、フェニルプロピレングリコール、メチルテトラグリコール、ポリグリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、ジエチレングリコールジブチルエーテル等が挙げられる。
As amines, ammonia, ethylenediamine, triethylenetetramine, diisopropanolamine, triethanolamine, monoethanolamine, diethanolamine, monoisopropanolamine, triisopropanolamine, diethylenetriamine, diethylamine, dibutylamine, hexahydroaniline, pentaethylene Examples include hexamine, allylamine, 2-aminopropanol, 3-aminopropanol, 4-aminobutanol, 4-methylaminobutanol, and ethylaminoethylamine.
As glycols, ethylene glycol, diethylene glycol, propylene glycol, methyl diglycol, allyl glycol, isobutyl glycol, butyl diglycol, isobutyl diglycol, methyl triglycol, butyl triglycol, glycerin, butylpropylene glycol, phenylpropylene glycol, methyl Examples include tetraglycol, polyglycol dimethyl ether, dipropylene glycol dimethyl ether, and diethylene glycol dibutyl ether.
なお、本実施形態の銅及び銅合金用表面処理剤を水溶液として、これを銅又は銅合金の表面に塗布又はスプレー等による散布、若しくは、上記の水溶液に銅又は銅合金を浸漬することにより、表面処理することが好ましいものである。 In addition, the surface treatment agent for copper and copper alloy of this embodiment is used as an aqueous solution, and this is applied to the surface of copper or copper alloy by spraying or spraying, or by immersing copper or copper alloy in the above aqueous solution, A surface treatment is preferred.
以下に実施例により本発明をさらに説明する。本発明に係る銅及び銅合金用表面処理剤の配合の代表的な組合せ及び添加量と、変色防止性能を評価する結露サイクル試験及び耐硫化ガス試験の結果と、乾燥残渣性を評価するスポット試験の結果とを表１〜８に示す。また、表９〜１２に、比較例の銅及び銅合金用表面処理剤の配合の代表的な組合せ及び添加量と、変色防止性能を評価する結露サイクル試験及び耐硫化ガス試験の結果と、乾燥残渣性を評価するスポット試験の結果とを示す。 The following examples further illustrate the present invention. Typical combinations and addition amounts of surface treatment agents for copper and copper alloys according to the present invention, results of condensation cycle test and anti-sulfur gas test for evaluating discoloration prevention performance, and spot test for evaluating dry residue properties The results are shown in Tables 1-8. Tables 9 to 12 show typical combinations and addition amounts of the surface treatment agents for copper and copper alloys of comparative examples, the results of the condensation cycle test and the sulfurization gas test for evaluating discoloration prevention performance, and drying. The result of the spot test which evaluates residue property is shown.
次に、上記各試験について詳細に説明する。
なお、結露サイクル試験及び耐硫化ガス試験の前処理として、以下の変色防止処理を行うこととする。まず、試験に必要な数の銅及び銅合金試験片を２０重量％硫酸に室温にて３０秒浸漬させた後、流水１０秒、イオン交換水３秒で洗い流し、ブロア乾燥する。その後、これらの試験片を６０℃の表１〜１２に示した各表面処理剤の水溶液につき1つずつ３秒間浸漬させた後、試験片表面から布で表面処理剤の水溶液を拭取り、ブロア乾燥する。
Next, each test will be described in detail.
In addition, the following discoloration prevention treatment is performed as a pretreatment for the dew condensation cycle test and the sulfide gas test. First, the number of copper and copper alloy test pieces necessary for the test are immersed in 20% by weight sulfuric acid for 30 seconds at room temperature, then rinsed with running water for 10 seconds and ion-exchanged water for 3 seconds, and dried in a blower. Then, after immersing these test pieces one by one for each aqueous solution of each surface treatment agent shown in Tables 1 to 12 at 60 ° C. for 3 seconds, the aqueous solution of the surface treatment agent was wiped from the surface of the test piece with a cloth. dry.
（結露サイクル試験の方法）
上記変色防止処理に用いた銅及び銅合金用表面処理剤の種類毎に、上記変色防止処理した、それぞれ１００ｍｍ×１００ｍｍ×０．３ｍｍ片の無酸素銅、リン青銅及び黄銅の３枚の試験片を重ね合わせ、上下方向に９．８×１０５Ｐａの圧力をかけた状態とし、図１に示すグラフ（１サイクルを示している）の条件のサイクル試験環境に放置して、変色が認められるまでのサイクル数を計測した。
(Method of dew cycle test)
For each kind of surface treatment agent for copper and copper alloy used for the above-mentioned discoloration prevention treatment, three specimens of 100 mm × 100 mm × 0.3 mm pieces of oxygen-free copper, phosphor bronze and brass, respectively, subjected to the above discoloration prevention treatment Are placed in a state in which a pressure of 9.8 × 10 5 Pa is applied in the up and down direction, and is left in the cycle test environment of the conditions shown in the graph (showing one cycle) shown in FIG. The number of cycles until was measured.
（耐硫化ガス試験の方法）
ＪＥＩＤＡ２５に準拠する方法を行った。具体的には、デシケータ中に２±１ｐｐｍのＨ２Ｓガスを発生させ、上記変色防止処理した２０ｍｍ×８０ｍｍ×０．３ｍｍ片の無酸素銅、リン青銅及び黄銅のそれぞれを４０℃で２０分間放置し、変色部分の面積を測定した。
(Sulfide gas test method)
A method based on JEIDA25 was performed. Specifically, 2 ± 1 ppm of H 2 S gas was generated in the desiccator, and each of 20 mm × 80 mm × 0.3 mm pieces of oxygen-free copper, phosphor bronze and brass subjected to the above discoloration prevention treatment at 40 ° C. for 20 minutes. The area of the discolored portion was measured by allowing it to stand.
（スポット試験の方法）
２０重量％の硫酸で酸洗した試験片に各銅及び銅合金用表面処理剤の水溶液を０．１ｍｌ滴下し、６０℃で６０分間乾燥させて、表面に残る残渣を観察した。
(Spot test method)
0.1 ml of each copper and copper alloy surface treatment solution was dropped on a test piece pickled with 20% by weight sulfuric acid and dried at 60 ° C. for 60 minutes, and the residue remaining on the surface was observed.
なお、表１〜１２における特性評価結果の表示は、以下のような基準によった。また、無酸素銅、リン青銅及び黄銅のそれぞれの試験結果は同様のものとなったので、１つにまとめて表示した。即ち、それぞれの記号には、無酸素銅、リン青銅及び黄銅の３つの試験結果が含まれていることとなっている。
（結露サイクル試験：表１〜１２では「結露」と表している）
◎：３１サイクル以上変色なし ○：２１〜３０サイクルで変色
△：１１〜２０サイクルで変色 ×：１０サイクル以下で変色
（耐硫化ガス試験：表１〜１２では「耐Ｈ２Ｓ」と表している）
◎：０〜２０％変色 ○：２１〜４０％変色
△：４１〜６０％変色 ×：６１％以上変色
（スポット試験：表１〜１２では「スポット」と表している）
◎：全く残渣は認められない ○：ごく僅かの残渣が認められる
△：少量の残渣が認められる ×：明らかな残渣が認められる
In addition, the display of the characteristic evaluation result in Tables 1-12 was based on the following criteria. Moreover, since the test results of oxygen-free copper, phosphor bronze, and brass were the same, they were collectively displayed. That is, each symbol includes three test results of oxygen-free copper, phosphor bronze, and brass.
(Condensation cycle test: In Tables 1 to 12, "condensation" is indicated)
◎: No change in color for 31 cycles or more ○: Change in color in 21 to 30 cycles Δ: Change in color in 11 to 20 cycles ×: Change in color in 10 cycles or less (sulfurization gas test: In Tables 1 to 12, expressed as “H 2 S resistance” Yes)
◎: 0 to 20% color change ○: 21 to 40% color change Δ: 41 to 60% color change ×: 61% or more color change (Spot test: In Tables 1 to 12, "spot" is indicated)
◎: No residue is observed at all ○: Very little residue is observed △: A small amount of residue is observed ×: Clear residue is observed
また、各表において、ＢＴはベンゾトリアゾール、ＴＴはトリルトリアゾール、ＣＢＴはカルボキシベンゾトリアゾール、ＴＥＡはトリエタノールアミン、ＤＩＰＡはジイソプロパノールアミン、ＰＧはプロピレングリコール、ＭＤＧはメチルジグリコールを示す。また、各物質の数値の単位はｐｐｍである。 In each table, BT represents benzotriazole, TT represents tolyltriazole, CBT represents carboxybenzotriazole, TEA represents triethanolamine, DIPA represents diisopropanolamine, PG represents propylene glycol, and MDG represents methyl diglycol. Moreover, the unit of the numerical value of each substance is ppm.
表１〜９（実施例）と表１０〜１４（比較例）とを比較すると、実施例に係る各銅及び銅合金用表面処理剤の水溶液は、比較例のものより変色防止性能を格段に高めることができることがわかる。乾燥残渣については、比較例に比べ、実施例のものは同等又はほとんどないものとなった。これにより、変色防止性能が付加された銅及び銅合金を提供できることがわかる。 Comparing Tables 1 to 9 (Examples) and Tables 10 to 14 (Comparative Examples), the aqueous solutions of the surface treatment agents for copper and copper alloys according to the Examples have far superior discoloration prevention performance than those of the Comparative Examples. It can be seen that it can be increased. About a dry residue, compared with the comparative example, the thing of the Example became a thing which is almost the same. Thereby, it turns out that the copper and copper alloy to which the discoloration prevention performance was added can be provided.
なお、本発明は、特許請求の範囲を逸脱しない範囲で設計変更できるものであり、上記実施形態や実施例に限定されるものではない。 The present invention can be changed in design without departing from the scope of the claims, and is not limited to the above-described embodiments and examples.
銅及び銅合金の表面処理時に残る銅及び銅合金用表面処理剤の水溶液を温風で吹き飛ばせば、表面にシミを残すことなく除去できる。また、表面処理によって銅及び銅合金の表面に変色防止皮膜ができるわけだが、この皮膜はアルカリ脱脂液や薄い酸で簡単に除去することができる。したがって、後行程の半田付け工程やメッキ工程に悪影響を及ぼすことがない。 If the aqueous solution of the copper and copper alloy surface treatment agent remaining during the surface treatment of copper and copper alloy is blown off with warm air, the surface can be removed without leaving a stain on the surface. Although it not possible that the surface to prevent discoloration film of copper and copper alloys by surface treatment, the coating can be easily removed with an alkaline degreasing solution or thin acid. Therefore, the soldering process and the plating process in the subsequent process are not adversely affected.
Claims (8)
１種以上のトリアゾール系化合物と、１種以上のアミン類と、下記一般式〔Ｉ〕で示されるアルケニルコハク酸群の中から選ばれる１種以上のアルケニルコハク酸とを含有することを特徴とする銅及び銅合金用表面処理剤。
(化１) ＣＨ２ＣＯＯＨ
｜
Ｒ−ＣＨ−ＣＯＯＨ ・・・・・〔Ｉ〕
（式中、Ｒは炭素原子数６〜３０のアルケニル基を表す。） A surface treatment agent for copper and copper alloy that forms a surface film in contact with the atmosphere,
It contains at least one triazole compound, at least one amine, and at least one alkenyl succinic acid selected from the alkenyl succinic acid group represented by the following general formula [I]. Surface treatment agent for copper and copper alloy.
(Chemical Formula 1) CH 2 COOH
｜
R-CH-COOH [I]
(In the formula, R represents an alkenyl group having 6 to 30 carbon atoms.)
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6156287A (en) * | 1984-08-27 | 1986-03-20 | Chiyoda Kagaku Kenkyusho:Kk | Rust preventive agent for metal |
| JPS63290284A (en) * | 1987-04-29 | 1988-11-28 | チバ−ガイキー アクチエンゲゼルシヤフト | Method for suppressing corrosion of copper or copper-containing alloy |
| JPH03232982A (en) * | 1990-02-08 | 1991-10-16 | Mitsubishi Oil Co Ltd | Rust preventive composition for metal |
| JPH0941167A (en) * | 1995-08-02 | 1997-02-10 | Fujikura Ltd | Rust-proofing treatment for copper or copper alloy material |
| JPH1161117A (en) * | 1997-08-27 | 1999-03-05 | Tokyo Fine Chem Kk | Rust preventive solution |
| JP2000273662A (en) * | 1999-03-19 | 2000-10-03 | Mitsubishi Materials Corp | Corrosion inhibiting/discoloration preventing agent for copper material |
| JP2002088488A (en) * | 2000-09-13 | 2002-03-27 | Kurita Water Ind Ltd | Anticorrosive composition for copper |
| JP2002129367A (en) * | 2000-10-26 | 2002-05-09 | Sanyo Chem Ind Ltd | Rust and corrosion inhibitor |
-
2004
- 2004-06-15 JP JP2004177213A patent/JP4628701B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6156287A (en) * | 1984-08-27 | 1986-03-20 | Chiyoda Kagaku Kenkyusho:Kk | Rust preventive agent for metal |
| JPS63290284A (en) * | 1987-04-29 | 1988-11-28 | チバ−ガイキー アクチエンゲゼルシヤフト | Method for suppressing corrosion of copper or copper-containing alloy |
| JPH03232982A (en) * | 1990-02-08 | 1991-10-16 | Mitsubishi Oil Co Ltd | Rust preventive composition for metal |
| JPH0941167A (en) * | 1995-08-02 | 1997-02-10 | Fujikura Ltd | Rust-proofing treatment for copper or copper alloy material |
| JPH1161117A (en) * | 1997-08-27 | 1999-03-05 | Tokyo Fine Chem Kk | Rust preventive solution |
| JP2000273662A (en) * | 1999-03-19 | 2000-10-03 | Mitsubishi Materials Corp | Corrosion inhibiting/discoloration preventing agent for copper material |
| JP2002088488A (en) * | 2000-09-13 | 2002-03-27 | Kurita Water Ind Ltd | Anticorrosive composition for copper |
| JP2002129367A (en) * | 2000-10-26 | 2002-05-09 | Sanyo Chem Ind Ltd | Rust and corrosion inhibitor |
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