JPH09111500A - Electrolytic etching solution of precipitation-hardening copper alloy product and electrolytic etching method - Google Patents
Electrolytic etching solution of precipitation-hardening copper alloy product and electrolytic etching methodInfo
- Publication number
- JPH09111500A JPH09111500A JP29598595A JP29598595A JPH09111500A JP H09111500 A JPH09111500 A JP H09111500A JP 29598595 A JP29598595 A JP 29598595A JP 29598595 A JP29598595 A JP 29598595A JP H09111500 A JPH09111500 A JP H09111500A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- electrolytic etching
- precipitation
- copper alloy
- alkali metal
- 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.)
- Granted
Links
- 238000000866 electrolytic etching Methods 0.000 title claims abstract description 35
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 13
- 238000004881 precipitation hardening Methods 0.000 title abstract 3
- 238000005530 etching Methods 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008139 complexing agent Substances 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims abstract description 11
- 150000008041 alkali metal carbonates Chemical class 0.000 claims abstract description 11
- -1 alkali metal salt Chemical class 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 9
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 235000015165 citric acid Nutrition 0.000 claims description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 5
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000174 gluconic acid Substances 0.000 claims description 5
- 235000012208 gluconic acid Nutrition 0.000 claims description 5
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 5
- 229960003330 pentetic acid Drugs 0.000 claims description 5
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- 239000011975 tartaric acid Substances 0.000 claims description 4
- 235000002906 tartaric acid Nutrition 0.000 claims description 4
- 239000011734 sodium Substances 0.000 description 12
- 238000007747 plating Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 229910000679 solder Inorganic materials 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N Alanine Chemical compound CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910017876 Cu—Ni—Si Inorganic materials 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000221561 Ustilaginales Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 229950010030 dl-alanine Drugs 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000004907 flux Effects 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
- 229910000833 kovar Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、析出強化型銅合金
からなるリードフレームやコネクタ等、各種電子部品の
ための電解エッチング液および電解エッチング方法に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic etching solution and an electrolytic etching method for various electronic parts such as lead frames and connectors made of precipitation strengthened copper alloy.
【０００２】[0002]
【従来の技術】半導体製品のリードフレームやコネクタ
の素材としては、当初、４２アロイ、コバール等の鉄−
ニッケル合金や、スズ、ニッケル、鉄等と銅との合金が
使われていたが、これら従来の銅合金は機械的強度が不
十分であるという問題点があったため、近年はその点を
改良されたいわゆる析出強化型銅合金が広く使われるよ
うになった。2. Description of the Related Art As a material for lead frames and connectors of semiconductor products, initially, 42 alloy, Kovar, etc.
Nickel alloys and alloys of copper with tin, nickel, iron, etc. have been used, but these conventional copper alloys have the problem of insufficient mechanical strength. So-called precipitation strengthened copper alloys have become widely used.
【０００３】析出強化型銅合金は、銅マトリックス中に
ベリリウム、ジルコニウム、チタン、ニッケル、鉄、ケ
イ素、スズ、リン等の元素を微細に析出させてなり、一
般的な銅合金なみの導電性を有しながら機械的強度がき
わめて優れているという特長がある。特にコルソン系合
金と呼ばれるＣu−Ｎi−Ｓi系合金は、電子部品材料と
して高い評価を得ている。The precipitation-strengthened copper alloy is formed by finely depositing elements such as beryllium, zirconium, titanium, nickel, iron, silicon, tin and phosphorus in a copper matrix, and has a conductivity similar to that of a general copper alloy. It has the feature of being extremely excellent in mechanical strength while having it. In particular, a Cu-Ni-Si-based alloy called a Corson alloy has been highly evaluated as a material for electronic parts.
【０００４】しかしながら、この合金で作られた電子部
品は表面清浄化のためのエッチングがかなり困難であ
る。すなわち、リードフレーム等の電子部品にはシリコ
ンチップの装着やプリント配線基板への実装を容易にす
るために、あるいは接触電気抵抗を低くするために、ハ
ンダめっき、金めっき、銀めっき等を施されるが、その
前処理の、表面酸化物層および加工変質層の除去のため
のエッチング処理に一般的な銅合金用のエッチング液を
使用すると、スマットと呼ばれる嵩高で不溶性の酸化物
を表面に生じやすい。スマットが生じたものは、その後
のめっき処理においてめっき皮膜の密着不良や異常析出
を起こし、使用に耐えない不良品となる。物性的には現
在最も好ましい材料とされるコルソン系合金はとりわけ
エッチングが困難であって、大量のスマットを生じやす
い。However, electronic parts made of this alloy are rather difficult to etch for surface cleaning. That is, electronic parts such as lead frames are subjected to solder plating, gold plating, silver plating, etc. in order to facilitate mounting of silicon chips and mounting on printed wiring boards, or to reduce contact electric resistance. However, when a general copper alloy etching solution is used for the pretreatment, that is, the etching treatment for removing the surface oxide layer and the work-affected layer, a bulky and insoluble oxide called smut is generated on the surface. Cheap. If smut is generated, defective adhesion or abnormal deposition of the plating film occurs in the subsequent plating process, and the product becomes a defective product that cannot be used. In terms of physical properties, the Corson alloy, which is the most preferable material at present, is particularly difficult to etch and tends to produce a large amount of smut.
【０００５】析出強化型銅合金製品をエッチング処理す
る方法としては、従来、フッ化物を加えた酸性液に浸漬
する方法が知られているが、フッ素イオンを含む排水の
処理費用が嵩むほか、リードフレームにフッ素イオンが
残留するとＩＣパッケージ内の電子回路に損傷を与える
という問題点がある。As a method of etching a precipitation-strengthened copper alloy product, a method of immersing it in an acid solution containing fluoride has been conventionally known. However, in addition to increasing the cost of treating wastewater containing fluoride ions, If fluorine ions remain in the frame, the electronic circuit in the IC package may be damaged.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、フッ
化物含有エッチング液を用いる場合のような不都合がな
くスマット発生のおそれもない、改良された析出強化型
銅合金製品用のエッチング液およびそれを使用するエッ
チング方法を提供することにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide an etching solution for an improved precipitation-strengthened copper alloy product which does not suffer from the disadvantages of using a fluoride-containing etching solution and the risk of smut formation. It is to provide an etching method using the same.
【０００７】[0007]
【課題を解決するための手段】本発明により提供された
析出強化型銅合金製品の電解エッチング液は、アルカリ
金属炭酸塩および錯化剤を含み、pＨが９〜13であり、
その組成が、５〜５０％の陽極電流効率で進行する電解
エッチング処理を可能にするものであることを特徴とす
る。The electrolytic etching solution for precipitation strengthened copper alloy products provided by the present invention comprises an alkali metal carbonate and a complexing agent, and has a pH of 9 to 13,
It is characterized in that its composition enables an electrolytic etching treatment which proceeds with an anode current efficiency of 5 to 50%.
【０００８】本発明はまた、上記本発明による電解エッ
チング液の中でも特に優れたものによる電解エッチング
方法、すなわちアルカリ金属炭酸塩および錯化剤を含
み、pHが９〜１３であり、前記錯化剤がクエン酸、グル
コン酸、酒石酸、リンゴ酸、ピロリン酸、トリポリリン
酸、エチレンジアミンテトラ酢酸、2-ヒドロキシエチル
エチレンジアミントリ酢酸、ジエチレントリアミンペン
タ酢酸、ニトリロトリ酢酸、トリエチレンテトラミンヘ
キサ酢酸、およびこれらの酸のアルカリ金属塩からなる
群から選ばれたものである電解エッチング液を用い、陽
極電流密度１〜３０Ａ/dm2、陽極電流効率５〜５０％の
電解エッチング処理を施すことを特徴とする析出強化型
銅合金製品の電解エッチング方法を提供するものであ
る。The present invention also provides an electrolytic etching method by using one of the above-mentioned electrolytic etching solutions of the present invention, which comprises an alkali metal carbonate and a complexing agent and has a pH of 9 to 13. Is citric acid, gluconic acid, tartaric acid, malic acid, pyrophosphoric acid, tripolyphosphoric acid, ethylenediaminetetraacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, and alkali metals of these acids A precipitation-strengthened copper alloy, characterized in that an electrolytic etching solution selected from the group consisting of salts is used for electrolytic etching treatment with an anode current density of 1 to 30 A / dm 2 and an anode current efficiency of 5 to 50%. A method for electrolytically etching a product is provided.
【０００９】[0009]
【発明の実施の形態】錯化剤を含むアルカリ性の電解エ
ッチング液は公知であるが、本発明の電解エッチング液
の最も特徴とするところは、析出強化型銅合金製品の電
解エッチングに使用したときの陽極電流効率が５〜５０
％となるように組成が選ばれることである。従来の銅合
金製品用エッチング液による電解エッチングでは陽極電
流効率が７０〜９５％程度になるから、本発明ではこれ
を意図的に低く抑えることになる。BEST MODE FOR CARRYING OUT THE INVENTION Although an alkaline electrolytic etching solution containing a complexing agent is known, the most significant feature of the electrolytic etching solution of the present invention is that it is used for electrolytic etching of a precipitation strengthened copper alloy product. Anode current efficiency of 5 to 50
The composition is chosen so that In the conventional electrolytic etching using an etching solution for copper alloy products, the anode current efficiency is about 70 to 95%, so the present invention intentionally suppresses this.
【００１０】これは、陽極電流効率が５０％以下で進行
する析出強化型銅合金製品の電解エッチングにおいては
スマットがほとんど生じないという本発明者らによる知
見に基づくものである。陽極電流効率が５０％以下に抑
制された状態でなぜスマットが生じなくなるのかはよく
判っていないが、スマットの主成分がケイ素、ニッケル
等の析出合金元素の酸化物であることを考えると、陽極
電流効率が高い状態では銅イオンの溶出が優先的に進行
したあと残された他の合金元素が酸化物に酸化されてス
マットを形成するのに対し陽極電流効率が低い状態では
銅以外の合金元素も銅と並行してイオン化し溶出するの
でスマットにならないものと思われる。This is based on the finding by the present inventors that smut hardly occurs in electrolytic etching of a precipitation-strengthened copper alloy product in which the anode current efficiency is 50% or less. It is not well known why smut does not occur when the anode current efficiency is suppressed to 50% or less, but considering that the main component of smut is an oxide of a precipitation alloy element such as silicon or nickel, In the state where the current efficiency is high, other alloying elements left after the preferential elution of copper ions are oxidized to form smuts, whereas in the state where the anode current efficiency is low, alloying elements other than copper It seems that smut does not become smut because it also ionizes and elutes in parallel with copper.
【００１１】もっとも、陽極電流効率が５％未満になる
と、エッチングそのものが著しく低能率になり、また、
陽極酸化による外観ムラやコゲと呼ばれる着色酸化物が
生じたりするので、必要以上に陽極電流効率を低下させ
る組成を選ぶことは避けなければならない。したがっ
て、特に望ましいのは、陽極電流効率が約１０〜４０％
になるように組成を選ぶことである。However, when the anode current efficiency is less than 5%, the etching itself becomes remarkably low in efficiency, and
Since unevenness in appearance due to anodic oxidation and colored oxides called kogation may occur, it is necessary to avoid selecting a composition that lowers the anodic current efficiency more than necessary. Therefore, it is particularly desirable that the anode current efficiency be about 10-40%.
The composition is selected so that
【００１２】陽極電流効率は、エッチング液の組成、特
に錯化剤の種類と濃度に依存する。したがって、本発明
の電解エッチング液に用いる錯化剤は、電解エッチング
処理における陽極電流効率に及ぼす影響を考慮して選択
することになる。The anodic current efficiency depends on the composition of the etching solution, especially the kind and concentration of the complexing agent. Therefore, the complexing agent used in the electrolytic etching solution of the present invention is selected in consideration of the influence on the anode current efficiency in the electrolytic etching treatment.
【００１３】多くの使用条件において前記好ましい陽極
電流効率によるエッチングを可能にする錯化剤の具体例
としては、次のようなものがある。 オキシカルボン酸類：クエン酸、グルコン酸、酒石
酸、リンゴ酸等、およびこれらの酸のアルカリ金属塩。 リンのオキシ酸：ピロリン酸、トリポリリン酸等、
およびこれらの酸のアルカリ金属塩。 アミノカルボン酸類：エチレンジアミンテトラ酢酸
（ＥＤＴＡ）、2-ヒドロキシエチルエチレンジアミント
リ酢酸（ＨＥＤＴＡ）、ジエチレントリアミンペンタ酢
酸（ＤＴＰＡ）、ニトリロトリ酢酸（ＮＴＡ）、トリエ
チレンテトラミンヘキサ酢酸（ＴＴＨＡ）等、およびこ
れらの酸のアルカリ金属塩。The following are specific examples of the complexing agent which enables etching with the above-mentioned preferable anode current efficiency under many conditions of use. Oxycarboxylic acids: citric acid, gluconic acid, tartaric acid, malic acid, etc., and alkali metal salts of these acids. Phosphorus oxyacids: pyrophosphoric acid, tripolyphosphoric acid, etc.
And alkali metal salts of these acids. Aminocarboxylic acids: ethylenediaminetetraacetic acid (EDTA), 2-hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), triethylenetetraminehexaacetic acid (TTHA), and the like of these acids. Alkali metal salt.
【００１４】エッチング液におけるこれらの錯化剤の濃
度は、約１０〜２００g/lが適当である。１０g/l未満で
はエッチングの進行がきわめて遅く、表面の酸化物層や
加工変質層を除去しきれない。また、２００g/lを超え
る高濃度にすることは、２００g/lに近い濃度ですでに
添加効果が飽和しているので経済的に不利になるだけで
ある。なお、錯化剤の中には濃度が高くなるとエッチン
グ処理中の陽極電流効率を高くするものがあるので、そ
のような錯化剤の場合は陽極電流効率を５０％以下に抑
えることができる範囲で用いることが必要になる。A suitable concentration of these complexing agents in the etching solution is about 10 to 200 g / l. If it is less than 10 g / l, the progress of etching is extremely slow, and the oxide layer and work-affected layer on the surface cannot be completely removed. In addition, a high concentration exceeding 200 g / l is economically disadvantageous because the effect of addition is already saturated at a concentration close to 200 g / l. It should be noted that some complexing agents increase the anode current efficiency during the etching process when the concentration is high. Therefore, in the case of such a complexing agent, the anode current efficiency can be suppressed to 50% or less. Need to be used in.
【００１５】本発明の電解エッチング液に錯化剤と共に
含有させるアルカリ金属炭酸塩は、錯化剤がその錯化合
物形成能を発揮し得るpＨに液を保つ作用、および、本
発明による好ましい電解エッチングを可能にする適度な
導電性を液に付与する作用をする。pＨを好適範囲に調
整するだけであれば他の炭酸塩や炭酸塩以外のアルカリ
金属塩、苛性アルカリ等も使用することができるが、本
発明の目的達成を可能にするためには電離定数が一定の
範囲内にあり且つアンモニウム塩のように錯化作用を有
するものではないことが必要である。pＨ調整剤として
アルカリ金属炭酸塩を使用することはかかる意味で必須
となる。The alkali metal carbonate contained in the electrolytic etching solution of the present invention together with the complexing agent has the function of keeping the solution at pH at which the complexing agent can exert its complex compound forming ability, and the preferred electrolytic etching according to the present invention. It has a function of imparting an appropriate conductivity to the liquid. Other carbonates, alkali metal salts other than carbonates, caustic alkalis, etc. can be used as long as the pH is adjusted to a suitable range. However, in order to achieve the object of the present invention, the ionization constant is It must be within a certain range and not have a complexing action like ammonium salts. The use of an alkali metal carbonate as a pH adjuster is essential in this sense.
【００１６】アルカリ金属炭酸塩としてはナトリウム
塩、カリウム塩、リチウム塩等をいずれも使用すること
ができ、その濃度は、５〜２００g/lが適当である。５g
/l未満では十分な導電性が得られず、２００g/lを超え
る多量を含有させることは意味がない。実用上望ましい
濃度は１０〜１００g/lである。なお、アルカリ金属の
重炭酸塩と苛性アルカリを併用することによりエッチン
グ液中でアルカリ金属炭酸塩を生じさせ、同じ効果を期
待してもよいことは言うまでもない。As the alkali metal carbonate, any of sodium salt, potassium salt, lithium salt and the like can be used, and the concentration thereof is appropriately 5 to 200 g / l. 5g
If it is less than / l, sufficient conductivity cannot be obtained, and it is meaningless to add a large amount exceeding 200 g / l. A practically desirable concentration is 10 to 100 g / l. Needless to say, the same effect may be expected by using an alkali metal bicarbonate and a caustic together to generate an alkali metal carbonate in the etching solution.
【００１７】本発明のエッチング液を用いる析出強化型
銅合金製品の電解エッチングは、常温〜約５５℃の温度
で、陽極電流密度を１〜３０Ａ/dm2程度とし、エッチン
グ量が約０.１〜１μmとなるように行うことが望まし
い。陽極電流密度が大きいほど、酸化物層や加工変質層
の除去速度すなわちエッチング速度が大きくなり、処理
に要する時間が短縮されるが、３０Ａ/dm2を超えるよう
な大きな電流密度にすると電流効率が低下してエッチン
グ速度は変わらなくなるので、電流密度を上げる利益が
ない。一方、電流密度が１Ａ/dm2未満では、エッチング
速度が小さすぎて実際的でない。また、必要以上にエッ
チング量を大きくすることも処理結果を悪くするので避
けなければならない。なお、陽極電流効率は処理温度が
低くなるにつれて高くなる傾向があり、実際の処理温度
において５〜５０％という制限範囲内に維持されること
が必要である。The electrolytic etching of the precipitation strengthened copper alloy product using the etching solution of the present invention is carried out at a temperature of room temperature to about 55 ° C., an anode current density of about 1 to 30 A / dm 2 , and an etching amount of about 0.1. It is desirable to carry out so as to have a thickness of 1 μm. The higher the anode current density, the higher the removal rate of the oxide layer and the work-affected layer, that is, the etching rate, and the shorter the time required for the treatment. However, if the current density is higher than 30 A / dm 2 , the current efficiency becomes higher. There is no benefit to increase the current density as it decreases and the etch rate remains the same. On the other hand, if the current density is less than 1 A / dm 2 , the etching rate is too small to be practical. In addition, it is necessary to avoid increasing the etching amount more than necessary because it will deteriorate the processing result. The anode current efficiency tends to increase as the treatment temperature decreases, and it is necessary to maintain the anode current efficiency within the limit range of 5 to 50% at the actual treatment temperature.
【００１８】本発明の電解エッチング液には、本発明の
目的達成を妨げない限り、ミスト防止、湿潤性向上等の
ための界面活性剤、その他任意の添加剤を含有させるこ
とができる。The electrolytic etching solution of the present invention may contain a surfactant for preventing mist, improving wettability, and other optional additives as long as the object of the present invention is not hindered.
【００１９】[0019]
【実施例】表１に記載した組成の電解エッチング液を用
い、温度５０℃、陽極電流密度５Ａ/dm2または１０Ａ/d
m2で、析出強化型銅合金のテストピースを陽極にして１
分間電解エッチングを行なった。エッチング試験に用い
たテストピースは、板状のコルソン系合金ＫＬＦ−１２
５（Ni 3.2％，Si 0.7％，Zn 0.3％，Sn 1.25％；神戸
製鋼所製品）を１８０℃で１０時間加熱してその表面に
酸化皮膜を生じさせたものである。EXAMPLE An electrolytic etching solution having the composition shown in Table 1 was used at a temperature of 50 ° C. and an anode current density of 5 A / dm 2 or 10 A / d.
At m 2 , use the precipitation-strengthened copper alloy test piece as the anode 1
Electrolytic etching was performed for a minute. The test piece used for the etching test is a plate-shaped Corson alloy KLF-12.
No. 5 (Ni 3.2%, Si 0.7%, Zn 0.3%, Sn 1.25%; Kobe Steel product) was heated at 180 ° C. for 10 hours to form an oxide film on the surface.
【００２０】処理結果を表２に示した。なお、試験結果
の評価方法は次のとおりである。 エッチング量：重量法 陽極電流効率(％)＝エッチング前後の重量差÷理論
エッチング量×１００ ただし、理論エッチング量＝電流値(Ａ)×処理時間(秒)
×31.5÷96500 半田濡れ性：不活性型ロジン系フラックスを使用
し、２３０℃の共晶半田にテストピースを浸漬したとき
半田で被覆された面積を浸漬部面積に対する百分率で表
した。 めっき密着性：エッチング処理したテストピースに
厚さ１０μmの半田めっきを施し、１７５℃で２４時間
加熱した後、フクレの有無を顕微鏡により観察した（フ
クレを生じなかったものを“良好”、フクレが発生した
ものを“不良”と表示した。）。The treatment results are shown in Table 2. The evaluation method of the test results is as follows. Etching amount: gravimetric method Anode current efficiency (%) = weight difference before and after etching / theoretical etching amount × 100 where theoretical etching amount = current value (A) × processing time (sec)
× 31.5 ÷ 96500 Solder wettability: When an inactive rosin-based flux was used and a test piece was immersed in eutectic solder at 230 ° C., the area covered with the solder was expressed as a percentage of the area of the immersed portion. Plating adhesion: Solder plating with a thickness of 10 μm was applied to an etched test piece and heated at 175 ° C. for 24 hours, and then observed with a microscope for the presence or absence of blisters. The generated one was displayed as "bad".)
【００２１】[0021]
【表１】 エッチング液組成および電解条件 陽極電流密度 アルカリ 錯化剤 （Ａ/dm2） （濃度 g/l） pＨ 濃度 （g/l） 実施例１ １０ 炭酸Ｎa（50） 11.4 リンゴ酸Ｎa（50） 〃 ２ １０ 炭酸Ｋ（50） 11.4 クエン酸Ｎa（50） 〃 ３ ５ 炭酸Ｎa（50） 11.3 グルコン酸Ｎa（80） 〃 ４ １０ 炭酸Ｎa（50） 10.4 トリポリリン酸Ｎa(100) 〃 ５ ５ 炭酸Ｋ（100） 11.1 ピロリン酸Ｋ（50） 〃 ６ １０ 炭酸Ｎa（100） 11.6 ＥＤＴＡ・４Ｎa（50） 〃 ７ １０ 炭酸Ｎa（100） 11.5 ＮＴＡ・３Ｎa（50） 比較例１ １０ ＮaＯＨ（20） 13.2 ＥＤＴＡ・４Ｎa（50） 〃 ２ １０ メタケイ酸Na(100） 13.0 ＥＤＴＡ・４Ｎa（50） 〃 ３ １０ 炭酸Ｎa（50） 11.4 DL-アラニン（50） 〃 ４ １０ 炭酸ＮＨ4(50） 11.4 クエン酸Ｎa（50）[Table 1] Etching solution composition and electrolysis conditions Anode current density Alkali complexing agent (A / dm 2 ) (concentration g / l) pH concentration (g / l) Example 1 10 Carbonate Na (50) 11.4 Na malate ( 50) 〃 2 10 Carbonic acid K (50) 11.4 Citric acid Na (50) 〃 3 5 Carbonic acid Na (50) 11.3 Gluconic acid Na (80) 〃 4 10 Carbonic acid Na (50) 10.4 Tripolyphosphoric acid Na (100) 〃 55 Carbonate K (100) 11.1 Pyrophosphate K (50) 〃 6 10 Carbonate Na (100) 11.6 EDTA ・ 4Na (50) 〃 7 10 Carbonate Na (100) 11.5 NTA ・ 3Na (50) Comparative Example 1 10 NaOH (20) 13.2 EDTA ・ 4Na (50) 〃 2 10 Na metasilicate (100) 13.0 EDTA ・ 4Na (50) 〃 3 10 Carbonate Na (50) 11.4 DL-alanine (50) 〃 4 10 Carbonate NH 4 (50) 11.4 Citric acid Na (50)
【００２２】[0022]
【表２】 処理結果 電流効率 エッチング量 半田濡れ性 エッチング めっき （％） （μm） （％） 外観 密着性 実施例１ ２３ ０.５１ １００ 良好 良好 〃 ２ １６ ０.３５ １００ 良好 良好 〃 ３ ２２ ０.２４ １００ 良好 良好 〃 ４ ３４ ０.７４ １００ 良好 良好 〃 ５ ４７ ０.５２ １００ 良好 良好 〃 ６ ２０ ０.４４ １００ 良好 良好 〃 ７ ３６ ０.７９ １００ 良好 良好 比較例１ ２ ０.０４ ０ 水酸化銅皮膜生成 不良 〃 ２ ０ ０.００ ０ 茶褐色無光沢 不良 〃 ３ ９１ ２.０４ ０ スマット発生 不良 〃 ４ ５２ １.１２ ０ スマット発生 不良[Table 2] Treatment results Current efficiency Etching amount Solder wettability Etching Plating (%) (μm) (%) Appearance Adhesion Example 1 23 0.51 100 100 Good Good 〃 2 16 0.35 100 Good Good 〃 3 220 .24 100 good good 〃 4 34 0.74 100 good good 〃 5 47 47.52 100 good good good 〃 6 20 0.44 100 good good 〃 7 36 0.79 100 good good comparative example 1 2 0.040 0 water Copper oxide film formation failure 〃 2 0.00 0.00 0 brown brown matte failure 〃 3 91 2.04 0 smut generation failure 〃 4 52 1.12.0 smut generation failure
【００２３】[0023]
【発明の効果】上述のように、本発明によれば析出強化
型銅合金製品のめっき前処理としての電解エッチングを
比較的安価で安全な薬剤のみを使用して容易に行い、被
処理物の表面をきわめて好ましい状態に清浄化すること
が可能になる。As described above, according to the present invention, electrolytic etching as a pretreatment for plating of precipitation-strengthened copper alloy products can be easily performed by using only a relatively inexpensive and safe chemical, It makes it possible to clean the surface to a very favorable condition.
Claims (4)
液において、アルカリ金属炭酸塩および錯化剤を含み、
pＨが９〜１３であり、その組成が、５〜５０％の陽極
電流効率で進行する電解エッチング処理を可能にするも
のであることを特徴とする析出強化型銅合金製品の電解
エッチング液。1. An electrolytic etching solution for a precipitation-strengthened copper alloy product, which comprises an alkali metal carbonate and a complexing agent,
An electrolytic etching solution for a precipitation-strengthened copper alloy product, which has a pH of 9 to 13 and has a composition that enables an electrolytic etching treatment to proceed with an anode current efficiency of 5 to 50%.
液において、アルカリ金属炭酸塩および錯化剤を含み、
pＨが９〜１３であり、前記錯化剤がクエン酸、グルコ
ン酸、酒石酸、リンゴ酸、ピロリン酸、トリポリリン
酸、エチレンジアミンテトラ酢酸、2-ヒドロキシエチル
エチレンジアミントリ酢酸、ジエチレントリアミンペン
タ酢酸、ニトリロトリ酢酸、トリエチレンテトラミンヘ
キサ酢酸、およびこれらの酸のアルカリ金属塩からなる
群から選ばれたものであり、それにより５〜５０％の陽
極電流効率で進行する電解エッチング処理を可能にする
ものであることを特徴とする析出強化型銅合金製品の電
解エッチング液。2. An electrolytic etching solution for a precipitation-strengthened copper alloy product, which comprises an alkali metal carbonate and a complexing agent,
The pH is 9 to 13, and the complexing agent is citric acid, gluconic acid, tartaric acid, malic acid, pyrophosphoric acid, tripolyphosphoric acid, ethylenediaminetetraacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, tritriacetic acid. It is selected from the group consisting of ethylenetetraminehexaacetic acid and alkali metal salts of these acids, which enables an electrolytic etching treatment that proceeds with an anode current efficiency of 5 to 50%. An electrolytic etching solution for precipitation strengthened copper alloy products.
み、pＨが９〜１３であり、前記錯化剤がクエン酸、グ
ルコン酸、酒石酸、リンゴ酸、ピロリン酸、トリポリリ
ン酸、エチレンジアミンテトラ酢酸、2-ヒドロキシエチ
ルエチレンジアミントリ酢酸、ジエチレントリアミンペ
ンタ酢酸、ニトリロトリ酢酸、トリエチレンテトラミン
ヘキサ酢酸、およびこれらの酸のアルカリ金属塩からな
る群から選ばれたものである電解エッチング液を用い、
陽極電流密度１〜３０Ａ/dm2、陽極電流効率５〜５０％
の電解エッチング処理を施すことを特徴とする析出強化
型銅合金製品の電解エッチング方法。3. An alkali metal carbonate and a complexing agent, having a pH of 9 to 13, wherein the complexing agent is citric acid, gluconic acid, tartaric acid, malic acid, pyrophosphoric acid, tripolyphosphoric acid, ethylenediaminetetraacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, and using an electrolytic etching solution selected from the group consisting of alkali metal salts of these acids,
Anode current density 1-30 A / dm 2 , anode current efficiency 5-50%
A method for electrolytically etching a precipitation-strengthened copper alloy product, which comprises performing the electrolytic etching process according to claim 1.
で電解エッチング処理を施すことを特徴とする請求項３
記載の析出強化型銅合金製品の電解エッチング方法。4. The electrolytic etching treatment is performed in a range where the etching amount is 0.1 to 1 μm.
A method for electrolytically etching a precipitation-strengthened copper alloy product as described.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29598595A JP3500239B2 (en) | 1995-10-20 | 1995-10-20 | Electrolytic etching solution and electrolytic etching method for precipitation strengthened copper alloy products |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29598595A JP3500239B2 (en) | 1995-10-20 | 1995-10-20 | Electrolytic etching solution and electrolytic etching method for precipitation strengthened copper alloy products |
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| Publication Number | Publication Date |
|---|---|
| JPH09111500A true JPH09111500A (en) | 1997-04-28 |
| JP3500239B2 JP3500239B2 (en) | 2004-02-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004645A1 (en) * | 2005-07-05 | 2007-01-11 | The Furukawa Electric Co., Ltd. | Copper alloy for electronic equipment and process for producing the same |
-
1995
- 1995-10-20 JP JP29598595A patent/JP3500239B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007004645A1 (en) * | 2005-07-05 | 2007-01-11 | The Furukawa Electric Co., Ltd. | Copper alloy for electronic equipment and process for producing the same |
| US7946022B2 (en) | 2005-07-05 | 2011-05-24 | The Furukawa Electric Co., Ltd. | Copper alloy for electronic machinery and tools and method of producing the same |
| TWI408241B (en) * | 2005-07-05 | 2013-09-11 | Furukawa Electric Co Ltd | Copper alloy for electronic machinery and tools and method of producing the same |
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| Publication number | Publication date |
|---|---|
| JP3500239B2 (en) | 2004-02-23 |
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