JPH09228075A - Selective nickel peeling liquid and peeling method using the same - Google Patents
Selective nickel peeling liquid and peeling method using the sameInfo
- Publication number
- JPH09228075A JPH09228075A JP6163496A JP6163496A JPH09228075A JP H09228075 A JPH09228075 A JP H09228075A JP 6163496 A JP6163496 A JP 6163496A JP 6163496 A JP6163496 A JP 6163496A JP H09228075 A JPH09228075 A JP H09228075A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- acid
- copper
- alloy
- stripping solution
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 109
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 title abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 20
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910001128 Sn alloy Inorganic materials 0.000 claims abstract description 6
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 40
- 238000007747 plating Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000975 dye Substances 0.000 claims description 15
- -1 halogen ion Chemical class 0.000 claims description 15
- 229910001174 tin-lead alloy Inorganic materials 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- QCGOYKXFFGQDFY-UHFFFAOYSA-M 1,3,3-trimethyl-2-[3-(1,3,3-trimethylindol-1-ium-2-yl)prop-2-enylidene]indole;chloride Chemical compound [Cl-].CC1(C)C2=CC=CC=C2N(C)\C1=C\C=C\C1=[N+](C)C2=CC=CC=C2C1(C)C QCGOYKXFFGQDFY-UHFFFAOYSA-M 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- SPXOTSHWBDUUMT-UHFFFAOYSA-N 138-42-1 Chemical compound OS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 SPXOTSHWBDUUMT-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- YTZPUTADNGREHA-UHFFFAOYSA-N 2h-benzo[e]benzotriazole Chemical compound C1=CC2=CC=CC=C2C2=NNN=C21 YTZPUTADNGREHA-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- 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 2
- 239000000999 acridine dye Substances 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001000 anthraquinone dye Substances 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000000987 azo dye Substances 0.000 claims description 2
- 239000000981 basic dye Substances 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000001006 nitroso dye Substances 0.000 claims description 2
- 239000001007 phthalocyanine dye Substances 0.000 claims description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000001017 thiazole dye Substances 0.000 claims description 2
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001018 xanthene dye Substances 0.000 claims description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical group NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 claims 1
- 230000005764 inhibitory process Effects 0.000 claims 1
- ZTBANYZVKCGOKD-UHFFFAOYSA-M n-(2-chloroethyl)-n-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].C1=CC(N(CCCl)C)=CC=C1C=CC1=[N+](C)C2=CC=CC=C2C1(C)C ZTBANYZVKCGOKD-UHFFFAOYSA-M 0.000 claims 1
- 125000003226 pyrazolyl group Chemical group 0.000 claims 1
- 150000003852 triazoles Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 45
- 239000000203 mixture Substances 0.000 description 13
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 12
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- BMOKHTQIBPRXSL-UHFFFAOYSA-N 2h-benzotriazole;sodium Chemical compound [Na].C1=CC=CC2=NNN=C21 BMOKHTQIBPRXSL-UHFFFAOYSA-N 0.000 description 9
- 229940045996 isethionic acid Drugs 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000003851 azoles Chemical class 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- SEEZWGFVHCMHJF-UHFFFAOYSA-N 2-nitrosophenol Chemical compound OC1=CC=CC=C1N=O SEEZWGFVHCMHJF-UHFFFAOYSA-N 0.000 description 1
- KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- FBOZXECLQNJBKD-ZDUSSCGKSA-N L-methotrexate Chemical compound C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 FBOZXECLQNJBKD-ZDUSSCGKSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Weting (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、選択的なニッケル
剥離液に関し、更に詳細には、銅または銅合金および錫
または錫合金を殆ど侵すことなくニッケルのみを選択的
に剥離することのできる剥離液に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a selective nickel stripping solution, and more particularly to a stripping solution capable of selectively stripping only nickel with almost no attack on copper or copper alloy and tin or tin alloy. Regarding liquid.
【０００２】[0002]
【従来の技術】従来から、プリント基板では電気ニッケ
ルめっきや無電解ニッケルめっきが施されており、その
不要なニッケル皮膜を剥離するためにニッケル剥離液が
使用されている。 しかし、最近の電子材料としてのプ
リント基板や電子部品としての半導体は、ファイン化が
進むにつれその形成する素材も複合素材化し、従来のよ
うな比較的シンプルな処理薬品では不可能となってき
た。2. Description of the Related Art Conventionally, a printed circuit board has been electroplated with nickel or electroless nickel, and a nickel stripping solution has been used to strip an unnecessary nickel film. However, in recent years, printed circuit boards as electronic materials and semiconductors as electronic parts have become complex materials as they are made finer, and it has become impossible with conventional comparatively simple processing chemicals.
【０００３】すなわち、従来の剥離液は、下地素材上の
皮膜を剥離するいわゆる単一素材上の剥離液であり、複
合素材化した電子材料、例えば、プリント基板、セラミ
ックス基板や半導体分野であるＴＡＢ（テープオートマ
テックボンディング）、ＰＧＡ（ピングリッドアレ
ー）、ＢＧＡ（ボールグリッドアレー）などでは、数種
類の素材から特定の金属のみを選択的に剥離するには、
幾つかの問題点があり使用に適さなかった。That is, the conventional stripper is a so-called stripper for stripping a film on a base material, and is an electronic material made into a composite material, for example, a printed circuit board, a ceramic substrate, and TAB in the semiconductor field. (Tape Automatic Tech Bonding), PGA (Pin Grid Array), BGA (Ball Grid Array), etc.
There were some problems and it was not suitable for use.
【０００４】例えば、硝酸系のニッケル剥離液では、剥
離すべき金属の他、その下地素材である銅またはその合
金や錫またはその合金が侵されてしまうという問題があ
った。また、過酸化水素とフッ化物系のニッケル剥離液
の場合でも、錫または錫合金が侵されてしまう。 更
に、シアンアルカリやアミンアルカリに酸化剤を添加し
た物は、複合素材の有機レジストを膨潤し溶解してしま
うので不適であり、また、シアン系ニッケル剥離液は毒
性が高い問題があり、アミン錯体系のニッケル剥離液は
廃水処理性に難点があり、公害性が高いという問題があ
った。For example, the nitric acid-based nickel stripping solution has a problem that the base material copper or its alloy or tin or its alloy is attacked in addition to the metal to be stripped. Further, even in the case of hydrogen peroxide and a fluoride-based nickel stripping solution, tin or tin alloy is attacked. Further, a product obtained by adding an oxidizing agent to cyan alkali or amine alkali is not suitable because it swells and dissolves the organic resist of the composite material, and the cyan-based nickel stripper has a problem of high toxicity. The systematic nickel stripper has a problem in that it has a difficulty in treating wastewater and is highly polluting.
【０００５】また、特開昭５８−１０８７８５号公報で
は、硫酸とｍ−ニトロベンゼンスルホン酸を含む液で電
解剥離を行う方法が、特開昭５８−５８２８０号公報で
は、鉄イオンとヒドロキシカルボン酸を主成分とする硝
酸と過酸化水素の混合物が、特開平６−３２２５５９号
公報では、硝酸、硫酸、過酸化水素およびケトン化合物
を含有する剥離液がそれぞれ開示、報告されている。Further, in Japanese Patent Laid-Open No. 58-108785, a method of electrolytic stripping with a solution containing sulfuric acid and m-nitrobenzenesulfonic acid is disclosed, and in Japanese Patent Laid-Open No. 58-58280, iron ions and hydroxycarboxylic acid are removed. JP-A-6-322559 discloses and reports a stripping solution containing nitric acid, sulfuric acid, hydrogen peroxide and a ketone compound, which is a mixture of nitric acid and hydrogen peroxide as main components.
【０００６】更に、市販のニッケルおよびニッケル合金
の剥離液（エッチング液）としては、アルカリ性のエン
ストリップＮＰ（メルテックス社製）、メテックスＳＣ
Ｂ（マグダーミット社製）、トップリップＡＺ（奥野製
薬社製）、オキシストリップＯＳ−４５６（荏原ユージ
ライト社製）や酸性のエバストリップＳＴ−４１（荏原
ユージライト社製）、メルストリップＮ−９５０（メル
テックス社製）、メルストリップＨＮ−８４１（メルテ
ックス社製）などの浸漬剥離法が知られている。Furthermore, commercially available stripping solutions (etching solutions) for nickel and nickel alloys include alkaline Enstrip NP (manufactured by Meltex) and Metex SC.
B (Magdermit), Top Lip AZ (Okuno Pharmaceutical), Oxystrip OS-456 (Ebara Eugelite), acidic Ebastrip ST-41 (Ebara Eugelite), Melstrip N-950. Dipping and peeling methods such as (manufactured by Meltex) and Melstrip HN-841 (manufactured by Meltex) are known.
【０００７】ところで、従来の処理方法で行うと次のよ
うな欠点が見られ、いずれも複合素材からの選択的ニッ
ケル剥離液としては十分なものといい難かった。 例え
ば、特開昭５８−１０８７８５号公報の硫酸とｍ−ニト
ロベンゼンスルホン酸を含む液で電解剥離を行う方法
は、ニッケルを剥離する部分に電解のための通電接点を
新たに形成しなければ成らないという基本的な欠点があ
り、不適である。 また、特開昭５８−５８２８０号公
報では、鉄イオンとヒドロキシカルボン酸を主成分とす
る硝酸と過酸化水素の混合物が、特開平６−３２２５５
９号公報では、硝酸、硫酸、過酸化水素およびケトン化
合物を含有する剥離液で、いずれもが硝酸を含むため処
理複合素材の錫または錫合金を溶解する欠点がある。By the way, the following drawbacks were observed when the conventional treatment method was used, and it was difficult to say that any of them was sufficient as a selective nickel stripping solution from a composite material. For example, in the method of electrolytic stripping with a solution containing sulfuric acid and m-nitrobenzenesulfonic acid, which is disclosed in JP-A-58-108785, a current-carrying contact for electrolysis must be newly formed at a portion where nickel is stripped. It has the basic drawback of being unsuitable. Further, in Japanese Patent Laid-Open No. 58-58280, a mixture of nitric acid containing iron ions and hydroxycarboxylic acid as main components and hydrogen peroxide is disclosed in Japanese Laid-Open Patent Publication No. 6-32255.
According to Japanese Patent Publication No. 9, a stripping solution containing nitric acid, sulfuric acid, hydrogen peroxide and a ketone compound, all of which contains nitric acid, has a drawback of dissolving tin or tin alloy of the treated composite material.
【０００８】更に、上記市販ニッケル剥離液のうち、ア
ルカリ性のものは、処理複合素材のレジストを膨潤溶解
してしまい不適である。 また、酸性のタイプは、上記
問題はないが、無電解ニッケル（Ｎｉ−Ｐ）の剥離で黒
色のスマットが残り、スマット除去に後処理としてシア
ンやクロム酸などの毒性の高い処理薬品を必要としする
ため、実用性に乏しいものであった。Furthermore, among the above-mentioned commercially available nickel strippers, alkaline ones are not suitable because they swell and dissolve the resist of the treated composite material. In addition, the acidic type does not have the above problem, but black smut remains when the electroless nickel (Ni-P) is peeled off, and a highly toxic treatment chemical such as cyanide or chromic acid is required as a post-treatment for removing the smut. Therefore, it was poor in practicality.
【０００９】[0009]
【発明が解決しようとする課題】従って、複合素材素材
上から、他の金属あるいは素材に影響を与えず、ニッケ
ルのみを選択的に剥離できる剥離液の提供が求められて
いた。Therefore, there has been a demand for providing a stripping solution capable of selectively stripping only nickel from the composite material material without affecting other metals or materials.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、ニッケル
金属の選択的剥離液について、鋭意研究を行った結果、
酸性成分および酸化剤を主成分とし、これに特定な金属
溶解抑制剤を添加すれば、他の金属やレジスト等に影響
することなくニッケルまたはその合金皮膜を選択的に剥
離できることを見出し、本発明を完成した。Means for Solving the Problems The inventors of the present invention conducted extensive studies on a selective stripping solution for nickel metal, and as a result,
It has been found that nickel or its alloy coating can be selectively peeled off without affecting other metals or resists by adding a specific metal dissolution inhibitor to the acidic component and the oxidizing agent as the main components, and the present invention. Was completed.
【００１１】すなわち本発明の目的は、複合素材から、
ニッケルまたはその合金を剥離し、銅またはその合金、
錫またはその合金を剥離することなく、更に、複合素材
の有機レジストも侵さないことを特徴とする選択的ニッ
ケル剥離液を提供することである。また、本発明の他の
目的は、上記剥離液の一例である成分（ａ）〜（ｄ） （ａ） ハロゲンイオン成分を含まない無機酸または有
機酸、（ｂ） 酸化剤、（ｃ） 芳香族ニトロ化合物、
（ｄ） 金属溶解抑制剤、を含有する選択的ニッケル剥
離液を提供することである。That is, the object of the present invention is to obtain a composite material from
Peel off nickel or its alloy, copper or its alloy,
It is an object of the present invention to provide a selective nickel stripping solution which does not strip tin or its alloy and does not attack the organic resist of the composite material. Another object of the present invention is components (a) to (d) (a) an inorganic acid or organic acid containing no halogen ion component, (b) an oxidizing agent, and (c) an aroma which are examples of the above-mentioned stripping solution. Group nitro compounds,
(D) To provide a selective nickel stripping solution containing a metal dissolution inhibitor.
【００１２】[0012]
【発明の実施の形態】本発明の選択的ニッケル剥離液に
おいて、使用される（ａ）成分としては、硫酸、リン
酸、ホウ酸、炭酸等の無機酸およびギ酸、酢酸、プロピ
オン酸、シュウ酸、乳酸、リンゴ酸、酒石酸、クエン
酸、グリコール酸、スルファミン酸、アルカンスルホン
酸であるメタンスルホン酸、エタンスルホン酸、アルカ
ノールスルホン酸、芳香族スルホン酸とその誘導体であ
るフェノールスルホン酸、ベンゼンスルホン酸、イセチ
オン酸等のアルカノールスルホン酸等の有機酸が挙げら
れる。BEST MODE FOR CARRYING OUT THE INVENTION As the component (a) used in the selective nickel stripping solution of the present invention, inorganic acids such as sulfuric acid, phosphoric acid, boric acid, carbonic acid and formic acid, acetic acid, propionic acid, oxalic acid are used. , Lactic acid, malic acid, tartaric acid, citric acid, glycolic acid, sulfamic acid, alkanesulfonic acid methanesulfonic acid, ethanesulfonic acid, alkanolsulfonic acid, aromatic sulfonic acid and its derivative phenolsulfonic acid, benzenesulfonic acid And organic acids such as alkanol sulfonic acid such as isethionic acid.
【００１３】これらの（ａ）成分のうち、好ましいもの
としては、硫酸およびクエン酸が挙げられる。Of these components (a), preferred are sulfuric acid and citric acid.
【００１４】この（ａ）成分は、（ｂ）成分である酸化
剤や（ｃ）成分である芳香族ニトロ化合物で酸化された
ニッケルを溶解する作用をするものであり、例えば、硫
酸を使用する場合、その使用量は５０ｇ／ｌ〜３００ｇ
／ｌである。 この硫酸の濃度が５０ｇ／ｌより少ない
と剥離作用が弱く、３００ｇ／ｌより多いと酸度が強過
ぎて複合素材のレジストにダメージを与え、また、銅の
配線や銅合金フレームを過度にエッチングする場合があ
る。The component (a) has a function of dissolving nickel oxidized by the oxidizing agent which is the component (b) and the aromatic nitro compound which is the component (c). For example, sulfuric acid is used. In that case, the usage amount is 50 g / l to 300 g
/ L. If the concentration of sulfuric acid is less than 50 g / l, the peeling action is weak, and if it is more than 300 g / l, the acidity is too strong to damage the resist of the composite material, and the copper wiring and the copper alloy frame are excessively etched. There are cases.
【００１５】更に、クエン酸は本発明の酸化剤と金属抑
制剤との組合せにより、ニッケルを選択的に溶解し、ま
た、酸化剤で酸化された無電解ニッケルの剥離に効果が
あり、これを使用する場合の量は１００ｇ／ｌ〜５００
ｇ／ｌである。 この濃度が、１００ｇ／ｌより少ない
と剥離作用が弱く、５００ｇ／ｌを越える場合には、そ
れ以上の効果が期待できず実用上不経済である。Further, citric acid has an effect of selectively dissolving nickel by the combination of the oxidizing agent of the present invention and a metal inhibitor, and is also effective in removing electroless nickel oxidized by the oxidizing agent. The amount when used is 100 g / l to 500
g / l. If this concentration is less than 100 g / l, the peeling action is weak, and if it exceeds 500 g / l, no further effect can be expected and it is uneconomical in practice.
【００１６】また、成分（ｂ）である酸化剤は、ニッケ
ルを酸化してニッケルの剥離を促進するが、特に、成分
（ｃ）である芳香族ニトロ化合物の作用を助長する作用
を有するものである。 この酸化剤としては、過酸化水
素およびペルオキソ化合物であるペルオキソ２硫塩酸、
ペルオキソホウ酸塩等が挙げられる。 これらの配合量
は過酸化水素では２０ｍｌ／ｌ〜１５０ｍｌ／ｌが好ま
しく、配合量が２０ｍｌ／ｌ以下ではニッケルの黒色酸
化皮膜を十分に除去できず、また、１５０ｍｌ／ｌを越
えると複合素材の銅の配線や銅合金フレームを過度にエ
ッチングする場合がある。The oxidizer as the component (b) oxidizes nickel and promotes the exfoliation of nickel, and in particular, has an action of promoting the action of the aromatic nitro compound as the component (c). is there. As the oxidant, hydrogen peroxide and peroxodihydrochloric acid which is a peroxo compound,
Examples thereof include peroxoborate salts. The blending amount of hydrogen peroxide is preferably 20 ml / l to 150 ml / l. When the blending amount is 20 ml / l or less, the black oxide film of nickel cannot be sufficiently removed. The copper wiring and the copper alloy frame may be excessively etched.
【００１７】更に、成分（ｃ）である芳香族ニトロ化合
物は、ニッケルを酸化してニッケルの剥離を促進するも
のである。 この芳香族ニトロ化合物の例としては、ｏ
−、ｍ−、ｐ−ニトロベンゼンスルホン酸、ｏ−、ｍ
−、ｐ−ニトロ安息香酸、ｏ−、ｍ−、ｐ−ニトロアニ
リン、ｏ−、ｍ−、ｐ−ニトロフェノールおよびこれら
の塩が挙げられる。 この成分（ｃ）の配合量として
は、２０ｇ／ｌ〜１５０ｇ／ｌが好ましい。配合量が２
０ｇ／ｌ以下では、酸化効果が十分に発揮されずニッケ
ルの剥離速度が遅く、１５０ｇ／ｌを越えるとニッケル
が酸化され過ぎて黒色化し、剥離速度が遅くなることが
ある。Further, the aromatic nitro compound, which is the component (c), oxidizes nickel to promote the exfoliation of nickel. Examples of this aromatic nitro compound include o
-, M-, p-nitrobenzenesulfonic acid, o-, m
-, P-nitrobenzoic acid, o-, m-, p-nitroaniline, o-, m-, p-nitrophenol and salts thereof. The blending amount of this component (c) is preferably 20 g / l to 150 g / l. The amount is 2
When it is 0 g / l or less, the oxidation effect is not sufficiently exerted, and the nickel peeling rate is slow. When it exceeds 150 g / l, nickel is over-oxidized and blackened, and the peeling rate may be slow.
【００１８】本発明の（ｄ）成分である金属抑制剤のう
ち、第１抑制剤である有機染料は、酸性溶液に溶解可能
なものであり、特に、錫−鉛合金と銅−銅合金に作用し
て腐食抑制作用を奏する。 有機染料の例としては、ア
ゾ染料（アゾ基：−Ｎ＝Ｎ−）、アントラキノン染料、
インジゴ系染料、フタロシアニン染料、ジおよびトリフ
ェニルメタン染料、キサンテン染料、アクリジン染料、
アジン系染料、スチルベン染料、メチン系染料（メチン
結合：−ＣＨ＝、アゾメチン結合：−ＣＨ＝Ｎ−）、ニ
トロ及びニトロソ染料およびチアゾール染料が挙げられ
る。 このうち、塩基性染料のカチオン系染料が好まし
く、例えば、アイゼン・カチロン・イエロー（Aisen Ca
thilon Yellow；保土谷化学）ＧＬＨ、アイゼン・カチ
ロン・オレンジ（Aisen Cathilon Orange；保土谷化
学）ＲＨ、アイゼン・カチロン・ピンク（Aisen Cathil
on Pink；保土谷化学）ＦＧＨ、アイゼン・アストラ・
フロキシン（Aisen Astra Phloxine；保土谷化学）ＦＦ
などが好ましい。Among the metal inhibitors which are the component (d) of the present invention, the organic dye which is the first inhibitor can be dissolved in an acidic solution, and particularly in the tin-lead alloy and the copper-copper alloy. It works and exerts a corrosion inhibiting effect. Examples of organic dyes include azo dyes (azo group: -N = N-), anthraquinone dyes,
Indigo dyes, phthalocyanine dyes, di- and triphenylmethane dyes, xanthene dyes, acridine dyes,
Examples thereof include azine dyes, stilbene dyes, methine dyes (methine bond: —CH =, azomethine bond: —CH = N—), nitro and nitroso dyes, and thiazole dyes. Among these, basic dyes such as cationic dyes are preferable, and examples thereof include Aisen Catylon Yellow.
thilon Yellow; Hodogaya Chemical Co., Ltd. GLH, Aisen Cathilon Orange (Aisen Cathilon Orange); Aisen Cathilon Pink (Aisen Cathil)
on Pink; Hodogaya Chemical) FGH, Eisen Astra
Phloxine (Aisen Astra Phloxine; Hodogaya Chemical) FF
Are preferred.
【００１９】上記有機染料の添加量は１０〜１００ｍｇ
／ｌが好ましく、添加量を１０〜１００ｍｇ／ｌにする
のは、１０ｍｇ／ｌ以下では、複合素材の錫−鉛合金お
よび銅合金フレームの腐食抑制効果が小さく、１００ｍ
ｇ／ｌを越える場合には、それ以上の効果が期待できず
実用上不経済であるからである。The amount of the above organic dye added is 10 to 100 mg.
/ L is preferable, and the addition amount is set to 10 to 100 mg / l. When the amount is 10 mg / l or less, the corrosion inhibiting effect of the tin-lead alloy and copper alloy frame of the composite material is small, and 100 m
If it exceeds g / l, no further effect can be expected and it is uneconomical in practice.
【００２０】また、（ｄ）成分のうち、第２の金属抑制
剤となるアゾール類としては、ピラゾール、イミダゾー
ル、ベンゾトリアゾール、トリトリアゾール、ナフトト
リアゾール、メルカプトベンゾチアゾール、メルカプト
トリアゾールまたはベンズイミダゾール等が挙げられ
る。 このアゾール類の配合量は、０.５〜１０.０ｇ／
ｌが好ましく、配合量が０.５ｇ／ｌ以下では、複合素
材の銅配線や銅合金フレームおよび錫−鉛合金の腐食抑
制効果が小さく、１０.０ｇ／ｌを越える場合には、そ
れ以上の効果が期待できず実用上不経済である。Among the azoles as the second metal inhibitor in the component (d), pyrazole, imidazole, benzotriazole, tritriazole, naphthotriazole, mercaptobenzothiazole, mercaptotriazole, benzimidazole and the like can be mentioned. To be The amount of this azole compounded is 0.5 to 10.0 g /
1 is preferable, and when the compounding amount is 0.5 g / l or less, the corrosion inhibiting effect of the copper wiring, the copper alloy frame and the tin-lead alloy of the composite material is small, and when it exceeds 10.0 g / l, it is more than It is uneconomical in practice because the effect cannot be expected.
【００２１】本発明の選択的ニッケル剥離液の使用方法
は、成分（ａ）〜（ｄ）を上記の量で配合した水溶液
に、ニッケルを剥離する対象物を浸漬すれば良い。 こ
の浸漬の条件としては、３０〜４５℃程度の温度で、撹
拌は１５〜６０ｃｍ／ｍｉｎ程度の揺動撹拌とすれば良
い。 剥離液の寿命は、ニッケルの剥離速度の低下によ
り判断することができ、一般には、ニッケル剥離液中の
ニッケル濃度が５０ｇ／ｌ以上となった時点を目安とす
ればよい。The selective nickel stripping solution of the present invention may be used by immersing an object for stripping nickel in an aqueous solution containing the components (a) to (d) in the above amounts. As conditions for this immersion, the temperature may be about 30 to 45 ° C., and the stirring may be rocking stirring at about 15 to 60 cm / min. The life of the stripping solution can be judged by the decrease in the stripping rate of nickel, and generally, the time when the nickel concentration in the nickel stripping solution becomes 50 g / l or more may be used as a standard.
【００２２】また、本発明の選択的ニッケル剥離液は、
単にニッケルを剥離するのみでなく、その選択的なニッ
ケル剥離能を生かして積極的に電子部品や回路の形成に
利用することもできる。 例えば、まず、銅合金フレー
ムの表面にニッケルまたはニッケル合金皮膜を形成さ
せ、レジストで配線パターンを形成後、この上に電気銅
めっきにより銅配線パターンを得る。 次いで、先のレ
ジストを剥離除去後、２回目のレジストを施し、錫−鉛
合金めっきで電極ボールを形成する。 更に、この配線
と反対側（裏面）から銅合金フレーム面をエッチング
し、前述のニッケルめっき皮膜を露出させ、最後に、こ
のニッケルまたはニッケル合金皮膜を本発明の選択的ニ
ッケル剥離液に浸漬することにより、選択的に剥離し、
微細配線の電子部品、例えばＢＧＡフレームを製造する
ことができる。Further, the selective nickel stripping solution of the present invention is
Not only can nickel be peeled off, but also by utilizing its selective nickel peeling ability, it can be positively utilized for forming electronic parts and circuits. For example, first, a nickel or nickel alloy film is formed on the surface of a copper alloy frame, a wiring pattern is formed with a resist, and then a copper wiring pattern is obtained by electrolytic copper plating. Then, after removing the previous resist by stripping, a second resist is applied and an electrode ball is formed by tin-lead alloy plating. Further, the copper alloy frame surface is etched from the side opposite to this wiring (back surface) to expose the above nickel plating film, and finally this nickel or nickel alloy film is immersed in the selective nickel stripping solution of the present invention. With selective peeling,
It is possible to manufacture electronic components with fine wiring, for example, a BGA frame.
【００２３】更に、絶縁基材表面に銅箔を接着した銅箔
板、または化学的処理後無電解銅めっき上に電気銅めっ
きを施し導電膜を形成した絶縁基材表面に、有機レジス
トで配線パターンを形成後、露出した銅配線パターン部
分に電気ニッケルめっきまたは無電解ニッケルめっきを
施した配線パターンを形成する。同時に、このめっき配
線パターンには、電子部品を搭載する端子パターンが形
成されており、有機めっきレジストを使ってこの端子パ
ターン部のみに錫−鉛合金（はんだ）めっきを行った
後、有機めっきレジストを除去するとニッケルめっきと
錫−鉛合金による配線パターンが形成される。更に、こ
のめっきによる配線パターンをエッチングレジストとし
て用い、露出した銅箔のみをエッチング除去すると必要
な回路の形状が形成できる。最後に、ニッケルめっきの
みを選択的に除去し、電子部品の端子パターン部分に
は、錫−鉛合金めっきを残し、ニッケル下地の銅や錫−
鉛合金の下地銅をサイドエッチングせずに配線回路を形
成できる。Further, a copper foil plate in which a copper foil is adhered to the surface of the insulating base material or a surface of the insulating base material on which electroconductive copper plating is applied on electroless copper plating after chemical treatment to form a conductive film is wired with an organic resist. After forming the pattern, the exposed copper wiring pattern portion is subjected to electric nickel plating or electroless nickel plating to form a wiring pattern. At the same time, a terminal pattern for mounting electronic components is formed on this plated wiring pattern, and after tin-lead alloy (solder) plating is applied only to this terminal pattern part using the organic plating resist, the organic plating resist is used. When removed, a wiring pattern made of nickel plating and tin-lead alloy is formed. Further, the wiring pattern formed by this plating is used as an etching resist, and only the exposed copper foil is removed by etching, whereby the required circuit shape can be formed. Finally, only the nickel plating is selectively removed, and the tin-lead alloy plating is left on the terminal pattern part of the electronic component.
It is possible to form a wiring circuit without side etching the copper base of the lead alloy.
【００２４】[0024]
【作用】本発明の選択的ニッケル剥離液が、選択的にニ
ッケルを剥離する作用機序は、金属溶解抑制剤である有
機染料とアゾール類が銅やその合金あるいは錫やその合
金に吸着して保護するため、剥離液の有効成分である酸
類、酸化剤および芳香族ニトロ化合物がニッケルのみを
酸化し、この酸化ニッケルを有効成分の酸類で溶解する
ものと解されている。The mechanism of action of the selective nickel stripping solution of the present invention for selectively stripping nickel is that the organic dye, which is a metal dissolution inhibitor, and the azoles are adsorbed on copper or its alloy or tin or its alloy. For protection, it is understood that the acid, the oxidizing agent and the aromatic nitro compound, which are the active ingredients of the stripping solution, oxidize only nickel and the nickel oxide is dissolved by the acid of the active ingredient.
【００２５】[0025]
【実施例】次に実施例を挙げ、更に詳しく説明するが、
本発明はこれら実施例等になんら制約されるものではな
い。[Examples] Next, more detailed description will be given with reference to Examples.
The present invention is not limited to these examples.
【００２６】実 施 例 １ 下記組成により、ニッケル剥離液を調製した。 （ 組 成 ） 硫酸（９８％） １００ｇ／ｌ クエン酸 １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌExample 1 A nickel stripping solution having the following composition was prepared. (Composition) Sulfuric acid (98%) 100 g / l Citric acid 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l
【００２７】実 施 例 ２ 下記組成により、ニッケル剥離液を調製した。 硫 酸（９８％） １００ｇ／ｌ クエン酸 １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸ナトリ ６５ｇ／ｌ ウム アイゼン・アストラ・フロキシン ＦＦ ５０ｍｇ／ｌExample 2 A nickel stripping solution having the following composition was prepared. Sulfuric acid (98%) 100 g / l Citric acid 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid Natri 65 g / l Um Eisen Astra Phloxine FF 50 mg / l
【００２８】実 施 例 ３ 下記組成により、ニッケル剥離液を調製した。 硫酸（９８％） １００ｇ／ｌ クエン酸 １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌ アイゼン・アストラ・フロキシン ＦＦ ５０ｍｇ／ｌExample 3 A nickel stripping solution was prepared according to the following composition. Sulfuric acid (98%) 100 g / l Citric acid 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l Eisen Astra Phloxine FF 50 mg / l
【００２９】実 施 例 ４ 下記組成により、ニッケル剥離液を調製した。 硫酸（９８％） １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌExample 4 A nickel stripping solution was prepared according to the following composition. Sulfuric acid (98%) 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l
【００３０】実 施 例 ５ 下記組成により、ニッケル剥離液を調製した。 クエン酸 １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌExample 5 A nickel stripping solution having the following composition was prepared. Citric acid 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l
【００３１】実 施 例 ６ 下記組成により、ニッケル剥離液を調製した。 イセチオン酸（７０％） １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌ アイゼン・アストラ・フロキシンＦＦ ５０ｍｇ／ｌExample 6 A nickel stripping solution having the following composition was prepared. Isethionic acid (70%) 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l Eisen Astra Phloxine FF 50 mg / l
【００３２】実 施 例 ７ 下記組成により、ニッケル剥離液を調製した。 イセチオン酸（７０％） １００ｇ／ｌ クエン酸（９８％） １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌ アイゼン・アストラ・フロキシンＦＦ ５０ｍｇ／ｌExample 7 A nickel stripping solution was prepared according to the following composition. Isethionic acid (70%) 100 g / l Citric acid (98%) 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l Eisen Astra Phloxine FF 50 mg / l
【００３３】実 施 例 ８ 下記組成により、ニッケル剥離液を調製した。 イセチオン酸（７０％） １００ｇ／ｌ グリコール酸（９８％） １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌ アイゼン・アストラ・フロキシンＦＦ ５０ｍｇ／ｌExample 8 A nickel stripping solution having the following composition was prepared. Isethionic acid (70%) 100 g / l Glycolic acid (98%) 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l Eisen Astra Phloxine FF 50 mg / l
【００３４】実 施 例 ９ 下記組成により、ニッケル剥離液を調製した。 リン酸（９８％） １００ｇ／ｌ イセチオン酸（７０％） １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌ アイゼン・アストラ・フロキシンＦＦ ５０ｍｇ／ｌExample 9 A nickel stripping solution was prepared according to the following composition. Phosphoric acid (98%) 100 g / l Isethionic acid (70%) 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l Eisen Astra Phloxine FF 50 mg / l
【００３５】実 施 例 １０ 下記組成により、ニッケル剥離液を調製した。 硫 酸（９８％） １００ｇ／ｌ イセチオン酸（７０％） １００ｇ／ｌ 過酸化水素（３５％） ５０ｍｌ／ｌ ｍ−ニトロベンゼンスルホン酸 ６５ｇ／ｌ ナトリウム ベンゾトリアゾール ５ｇ／ｌ アイゼン・アストラ・フロキシンＦＦ ５０ｍｇ／ｌExample 10 A nickel stripping solution was prepared according to the following composition. Sulfuric acid (98%) 100 g / l Isethionic acid (70%) 100 g / l Hydrogen peroxide (35%) 50 ml / l m-Nitrobenzenesulfonic acid 65 g / l Sodium benzotriazole 5 g / l Eisen Astra Phloxine FF 50 mg / l
【００３６】比 較 例 １ ニッケル剥離液（特公平３−７７８７８号、実施例１） リ ン 酸（９０％） ５００ｍｌ／ｌ 硝 酸（６２％） １００ｍｌ／ｌ ｏ−ニトロソフェノール ０.５ｇ／ｌ （ 温 度 ６０℃ ）Comparative Example 1 Nickel stripping solution (Japanese Patent Publication No. 3-77878, Example 1) Phosphoric acid (90%) 500 ml / l Nitric acid (62%) 100 ml / l o-Nitrosophenol 0.5 g / l (Temperature 60 ℃)
【００３７】比 較 例 ２ ニッケル剥離液（特公平３−７７８７８号、実施例３） 硫 酸（９８％） ３００ｍｌ／ｌ 硝 酸（６２％） ３０ｍｌ／ｌ 酢 酸（９９％） ５０ｍｌ シュウ酸 １００ｇ／ｌ ｐ−ニトロフェニルヒドラジン ０.５ｇ／ｌ （ 温 度 ６０℃ ）Comparative Example 2 Nickel stripping solution (Japanese Patent Publication No. 3-77878, Example 3) Sulfuric acid (98%) 300 ml / l Nitric acid (62%) 30 ml / l Acetic acid (99%) 50 ml Oxalic acid 100 g / L p-nitrophenylhydrazine 0.5g / l (Temperature 60 ℃)
【００３８】比 較 例 ３ ニッケル剥離液（特開平６−５７４５４号、実施例３） 硝 酸（６７.５％） ２００ｇ／ｌ 過酸化水素（３５％） １０ｍｌ／ｌ 酢 酸（９９％） １００ｇ／ｌ ベンズトリアゾール ５ｇ／ｌ （ 温 度 ５０℃ ）Comparative Example 3 Nickel stripping solution (JP-A-6-57454, Example 3) Nitric acid (67.5%) 200 g / l Hydrogen peroxide (35%) 10 ml / l Acetic acid (99%) 100 g / L Benztriazole 5g / l (Temperature 50 ℃)
【００３９】比 較 例 ４ ニッケル剥離液（特開平６−５７４５４号、実施例２） 硝 酸（６７.５％） ２００ｇ／ｌ 過酸化水素（３５％） １０ｍｌ／ｌ プロピオン酸 １００ｇ／ｌ ベンズトリアゾール ５ｇ／ｌ （ 温 度 ５０℃ ）Comparative Example 4 Nickel stripping solution (JP-A-6-57454, Example 2) Nitric acid (67.5%) 200 g / l Hydrogen peroxide (35%) 10 ml / l Propionic acid 100 g / l Benztriazole 5g / l (Temperature 50 ℃)
【００４０】試 験 例 ニッケル剥離性試験：銅平板（２０×１０×０.５ｍ
ｍ）上に電気ニッケルめっきおよび錫−鉛合金めっきを
施したものを試料として、ニッケルの剥離試験を行っ
た。試料は、銅上にニッケルめっきを１０μｍの厚みで
施し、更にこのニッケル皮膜の半分をマスキングテープ
でマスキングしてから錫−鉛合金（９：１ はんだ）め
っきを１０μｍ施し、マスキングテープを除去したもの
を試験片とした。Test Example Nickel peelability test: Copper flat plate (20 × 10 × 0.5 m
A nickel peeling test was performed using a sample obtained by subjecting m) to electric nickel plating and tin-lead alloy plating. The sample was nickel plated on copper to a thickness of 10 μm, half of this nickel film was masked with masking tape, then tin-lead alloy (9: 1 solder) plating was 10 μm, and the masking tape was removed. Was used as the test piece.
【００４１】試験は、この試験片を実施例の剥離液に、
温度３５℃で５分間浸漬し、ニッケル皮膜の剥離の程
度、錫−鉛めっき層および銅素材の侵食の程度を目視で
観察した。 また、各剥離液の銅、錫および鉛の溶解性
を、銅平板あるいは錫−鉛合金めっき皮膜を直接浸漬し
（３５℃、５分間）、浸漬後の剥離液中の銅、錫および
鉛の量を原子吸光光度法により測定することにより行っ
た。 また、比較例１〜４のニッケル剥離剤について
も、温度を指定の温度に変更する以外は同様にしてニッ
ケル剥離性試験を行った。 この結果を下の表に示す。In the test, this test piece was used as the stripping solution of the example.
After immersion for 5 minutes at a temperature of 35 ° C., the degree of peeling of the nickel film and the degree of corrosion of the tin-lead plating layer and the copper material were visually observed. Further, the solubility of copper, tin and lead of each stripping solution was measured by directly immersing a copper plate or a tin-lead alloy plating film (35 ° C. for 5 minutes) to remove copper, tin and lead in the stripping solution after immersion. The amount was measured by the atomic absorption spectrophotometry. Further, with respect to the nickel release agents of Comparative Examples 1 to 4, the nickel release property test was conducted in the same manner except that the temperature was changed to the designated temperature. The results are shown in the table below.
【００４２】 [0042]
【００４３】この結果から明らかなように、本発明のニ
ッケル剥離液によれば、複合材料中からニッケルを選択
的に剥離することが可能である。As is clear from this result, the nickel stripping solution of the present invention can selectively strip nickel from the composite material.
【００４４】[0044]
【発明の効果】本発明によれば、複合素材上から選択的
にニッケルのみを剥離する剥離液が提供される。 この
剥離液は、単に不要なニッケル金属を剥離するために利
用できるのみならず、ファイン化した電子部品や回路を
製作するために、最もコストメリットがあり量産性の高
いウエット処理を提供することができるものである。According to the present invention, a stripping solution for selectively stripping only nickel from a composite material is provided. This stripper can be used not only to strip unnecessary nickel metal, but also to provide the most cost-effective and mass-productive wet treatment for producing fine electronic components and circuits. It is possible.
【００４５】例えば、従来の半導体ＢＧＡ（ボールグリ
ッドアレー）は主にドライ法で製作されていたが、この
方法は真空チャンバーを用いる枚葉処理となり、処理ご
とに真空チャンバーへ処理物挿入、真空チャンバー排
気、真空チャンバー大気開放、処理物取り出しの工程を
とるため、大掛かりな真空設備を必要とし、量産向きで
なく高コストであった。For example, the conventional semiconductor BGA (ball grid array) was mainly manufactured by a dry method, but this method is a single-wafer processing using a vacuum chamber, and the processing object is inserted into the vacuum chamber for each processing and the vacuum chamber is processed. Since the steps of exhausting, opening the atmosphere in the vacuum chamber, and taking out the processed product are required, a large-scale vacuum facility is required, which is not suitable for mass production and is expensive.
【００４６】これに対し、本発明の選択的ニッケル剥離
液を用いるウエット法によれば、大気下、４０℃付近の
温度で半導体ＢＧＡを製作することが可能になり、コス
トを大幅に引き下げることが可能となる。 従って、フ
ァイン化の限界が見えてきたＱＦＰ半導体パッケージに
対し、生産コスト面で不利であったＢＧＡパッケージを
経済的に製造することが可能となった。On the other hand, according to the wet method using the selective nickel stripping solution of the present invention, it becomes possible to manufacture the semiconductor BGA at a temperature of about 40 ° C. in the atmosphere, and the cost can be drastically reduced. It will be possible. Therefore, it becomes possible to economically manufacture the BGA package, which is disadvantageous in terms of production cost, as compared with the QFP semiconductor package which has reached the limit of fineness.
【００４７】同様に、電子分野であるプリント基板、セ
ラミックス基板や半導体分野であるＴＡＢ（テープオー
トマテックボンディング）、ＰＧＡ（ピングリッドアレ
ー）などで、数種類の素材からなる複合材で回路パター
ンやバンプ形成をするときに、ニッケルまたはその合金
のみを選択的、優先的に溶解剥離し、所望の電子部品の
配線回路を形成することも可能となった。 以 上Similarly, in a printed circuit board in the electronic field, a ceramics substrate, and TAB (tape automatic bonding) in the semiconductor field, PGA (pin grid array), etc., circuit patterns and bumps are formed by a composite material of several kinds of materials. It has also become possible to selectively and preferentially melt and exfoliate only nickel or an alloy thereof to form a wiring circuit of a desired electronic component. that's all
Claims (13)
を剥離し、銅またはその合金、錫またはその合金を剥離
することなく、更に、複合素材の有機レジストも侵さな
いことを特徴とする選択的ニッケル剥離液。1. A selective nickel characterized by exfoliating nickel or an alloy thereof from a composite material without exfoliating copper or an alloy thereof, tin or an alloy thereof, and further not attacking an organic resist of the composite material. Stripping solution.
機酸、 （ｂ） 酸化剤、 （ｃ） 芳香族ニトロ化合物、 （ｄ） 金属溶解抑制剤、 を含有する請求項第１項記載の選択的ニッケル剥離液。2. The following components (a) to (d) (a) an inorganic or organic acid containing no halogen ion component, (b) an oxidizing agent, (c) an aromatic nitro compound, (d) metal dissolution inhibition The selective nickel stripping solution according to claim 1, further comprising an agent.
ない無機酸または有機酸が、硫酸、リン酸、ホウ酸、炭
酸、ギ酸、酢酸、プロピオン酸、シュウ酸、乳酸、リン
ゴ酸、酒石酸、クエン酸、グリコール酸、スルファミン
酸、アルカンスルホン酸、芳香族スルホン酸またはアル
カノールスルホン酸から選ばれたものである請求項第１
項または第２項記載の選択的ニッケル剥離液。3. The inorganic or organic acid containing no halogen ion component of component (a) is sulfuric acid, phosphoric acid, boric acid, carbonic acid, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, malic acid, tartaric acid, A compound selected from citric acid, glycolic acid, sulfamic acid, alkane sulfonic acid, aromatic sulfonic acid or alkanol sulfonic acid.
Item 8. The selective nickel stripping solution according to Item 2 or Item 2.
はペルオキソ化合物である請求項第２項記載の選択的ニ
ッケル剥離液。4. The selective nickel stripping solution according to claim 2, wherein the oxidizing agent of component (b) is hydrogen peroxide or a peroxo compound.
−、ｍ−、ｐ−ニトロベンゼンスルホン酸、ｏ−、ｍ
−、ｐ−ニトロ安息香酸、ｏ−、ｍ−、ｐ−ニトロアニ
リン、ｏ−、ｍ−、ｐ−ニトロフェノールまたはこれら
の塩から選ばれたものである請求項第２項記載の選択的
ニッケル剥離液。5. The aromatic nitro compound of component (c) is o
-, M-, p-nitrobenzenesulfonic acid, o-, m
The selective nickel according to claim 2, which is selected from-, p-nitrobenzoic acid, o-, m-, p-nitroaniline, o-, m-, p-nitrophenol or salts thereof. Stripping solution.
制剤と第２抑制剤よりなるものである請求項第２項記載
の選択的ニッケル剥離液。6. The selective nickel stripping solution according to claim 2, wherein the metal dissolution inhibitor of component (d) comprises a first inhibitor and a second inhibitor.
ン染料、インジゴ系染料、フタロシアニン染料、ジおよ
びトリフェニルメタン染料、キサンテン染料、アクリジ
ン染料、アジン系染料、スチルベン染料、メチン系染
料、ニトロ及びニトロソ染料、チアゾール染料から選ば
れたものである請求項第５項記載の選択的ニッケル剥離
液。7. The first inhibitor is an azo dye, anthraquinone dye, indigo dye, phthalocyanine dye, di- and triphenylmethane dye, xanthene dye, acridine dye, azine dye, stilbene dye, methine dye, nitro and The selective nickel stripping solution according to claim 5, which is selected from nitroso dyes and thiazole dyes.
料であるアイゼン・カチロン・イエロー（Aisen Cathil
on Yellow）ＧＬＨ、アイゼン・カチロン・オレンジ（A
isen Cathilon Orange）ＲＨ、アイゼン・カチロン・ピ
ンク（AisenCathilon Pink）ＦＧＨおよびアイゼン・ア
ストラ・フロキシン（Aisen AstraPhloxine）ＦＦから
選ばれたものである請求項第６項記載の選択的ニッケル
剥離液。8. The first inhibitor is a basic dye-based cationic dye, Aisen Cathil Yellow.
on Yellow) GLH, Eisen Catillon Orange (A
The selective nickel stripping solution according to claim 6, which is selected from isen Cathilon Orange RH, Aisen Cathilon Pink FGH and Aisen AstraPhloxine FF.
ゾール類である請求項第６項記載の選択的ニッケル剥離
液。9. The selective nickel stripping solution according to claim 6, wherein the second inhibitor is an azole or a triazole.
ール、ベンゾトリアゾール、トリトリアゾール、ナフト
トリアゾール、メルカプトベンゾチアゾール、メルカプ
トトリアゾールまたはベンズイミダゾールから選ばれた
ものである請求項第６項記載の選択的ニッケル剥離液。10. The selective nickel according to claim 6, wherein the second inhibitor is selected from pyrazole, imidazole, benzotriazole, tritriazole, naphthotriazole, mercaptobenzothiazole, mercaptotriazole or benzimidazole. Stripping solution.
項記載の選択的ニッケル剥離液を用い、銅または銅合
金、錫または錫合金およびニッケルからなる複合素材か
ら、実質的に銅または銅合金および錫または錫合金を侵
すことなく、ニッケルまたはその合金皮膜を０.５〜１.
０μｍ／分の速度で剥離する選択的ニッケル剥離方法。11. A composite material consisting of copper or a copper alloy, tin or a tin alloy, and nickel, which is substantially copper, using the selective nickel stripping solution according to any one of claims 1 to 9. Alternatively, nickel or its alloy film can be applied to 0.5 to 1.% without attacking copper alloy and tin or tin alloy.
A selective nickel stripping method stripping at a rate of 0 μm / min.
電子回路の作製方法。 （i） 絶縁基材表面に銅箔を接着した銅箔板に、有機め
っきレジストで第一の配線パターンを形成後、ニッケル
めっきを施す、 （ii） （i）で得られたニッケルめっき後の表面に、有
機めっきレジストを使って第二の配線パターンを形成
し、錫−鉛合金めっきを行なう、 （iii） 露出した銅部分をエッチング除去する、 （iv） （iii）で得られたニッケルめっきと錫−鉛合金
による回路配線を作成後、請求項第１項記載の選択的ニ
ッケル剥離液に浸漬し、ニッケル皮膜を選択的に剥離す
る。12. A method of manufacturing an electronic circuit, which comprises sequentially performing the following steps. (I) After forming a first wiring pattern with an organic plating resist on a copper foil plate having a copper foil adhered to the surface of an insulating base material, nickel plating is performed. (Ii) After the nickel plating obtained in (i) A second wiring pattern is formed on the surface using an organic plating resist, and tin-lead alloy plating is performed. (Iii) The exposed copper part is removed by etching. (Iv) The nickel plating obtained in (iii). After forming the circuit wiring with the tin-lead alloy, the nickel film is immersed in the selective nickel stripping solution according to claim 1 to selectively strip the nickel film.
電子部品もしくは電子回路の作製方法。 （i）銅または銅合金フレーム上にニッケルまたはニッ
ケル合金めっきを施す、 （ii） （i）で得られたニッケルまたはニッケル合金皮
膜上に、有機めっきレジストで第一の配線パターンを形
成後、銅めっきを施す、 （iii） （ii）で得られた銅めっき後の表面から、有機
めっきレジストを除去し、更に別の有機めっきレジスト
を使って第二の配線パターンを形成し、錫−鉛合金めっ
きを行なう、 （iv） 裏側の銅または銅合金フレーム部分をエッチン
グ除去する、 （v） （iv）で露出したニッケルめっきを、請求項第１
項記載の選択的ニッケル剥離液に浸漬し、ニッケル皮膜
を選択的に剥離する、 （vi） 有機めっきレジストを除去する。13. A method for manufacturing an electronic component or an electronic circuit, which comprises sequentially performing the following steps. (I) Nickel or nickel alloy plating is applied on the copper or copper alloy frame, (ii) Copper is formed on the nickel or nickel alloy film obtained in (i) with the organic wiring resist to form a first wiring pattern. Plating, (iii) removing the organic plating resist from the surface after copper plating obtained in (ii), forming a second wiring pattern using another organic plating resist, and tin-lead alloy Plating, (iv) etching away the copper or copper alloy frame portion on the back side, (v) nickel plating exposed in (iv),
The nickel film is selectively peeled by immersing in the selective nickel stripping solution described in the item (vi) The organic plating resist is removed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06163496A JP3540887B2 (en) | 1996-02-26 | 1996-02-26 | Selective nickel stripping solution and stripping method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06163496A JP3540887B2 (en) | 1996-02-26 | 1996-02-26 | Selective nickel stripping solution and stripping method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09228075A true JPH09228075A (en) | 1997-09-02 |
| JP3540887B2 JP3540887B2 (en) | 2004-07-07 |
Family
ID=13176833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06163496A Expired - Lifetime JP3540887B2 (en) | 1996-02-26 | 1996-02-26 | Selective nickel stripping solution and stripping method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3540887B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006060207A (en) * | 2004-08-03 | 2006-03-02 | Samsung Electronics Co Ltd | Etching solution and method of forming magnetic memory device utilizing it |
| JP2006286371A (en) * | 2005-03-31 | 2006-10-19 | Ngk Spark Plug Co Ltd | Method for manufacturing sparking plug |
| JP2009079902A (en) * | 2007-09-25 | 2009-04-16 | Yazaki Corp | Quantitative analysis method of nickel or nickel alloy plating layer |
| JP2014232874A (en) * | 2013-05-02 | 2014-12-11 | 富士フイルム株式会社 | Etching method, etchant and etchant kit used for the same, and method for manufacturing semiconductor substrate product |
| JP2014232873A (en) * | 2013-05-02 | 2014-12-11 | 富士フイルム株式会社 | Etching method, etchant used for the same, and method for manufacturing semiconductor substrate product |
| TWI464301B (en) * | 2008-01-11 | 2014-12-11 | Mec Co Ltd | Etching solution |
| CN112111740A (en) * | 2020-09-24 | 2020-12-22 | 深圳市松柏实业发展有限公司 | Removing liquid for nickel-phosphorus coating, preparation method and removing method for nickel-phosphorus coating |
| CN113957442A (en) * | 2021-02-01 | 2022-01-21 | 江苏悦锌达新材料有限公司 | Nickel removing liquid medicine for nickel electroplating anti-corrosion layer, preparation method and chemical nickel removing process |
-
1996
- 1996-02-26 JP JP06163496A patent/JP3540887B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006060207A (en) * | 2004-08-03 | 2006-03-02 | Samsung Electronics Co Ltd | Etching solution and method of forming magnetic memory device utilizing it |
| US8092698B2 (en) | 2004-08-03 | 2012-01-10 | Samsung Electronics Co., Ltd. | Methods of forming semiconductor devices formed by processes including the use of specific etchant solutions |
| JP2006286371A (en) * | 2005-03-31 | 2006-10-19 | Ngk Spark Plug Co Ltd | Method for manufacturing sparking plug |
| JP2009079902A (en) * | 2007-09-25 | 2009-04-16 | Yazaki Corp | Quantitative analysis method of nickel or nickel alloy plating layer |
| TWI464301B (en) * | 2008-01-11 | 2014-12-11 | Mec Co Ltd | Etching solution |
| JP2014232874A (en) * | 2013-05-02 | 2014-12-11 | 富士フイルム株式会社 | Etching method, etchant and etchant kit used for the same, and method for manufacturing semiconductor substrate product |
| JP2014232873A (en) * | 2013-05-02 | 2014-12-11 | 富士フイルム株式会社 | Etching method, etchant used for the same, and method for manufacturing semiconductor substrate product |
| US10435794B2 (en) | 2013-05-02 | 2019-10-08 | Fujifilm Corporation | Etching method, etching solution used in same, and production method for semiconductor substrate product |
| CN112111740A (en) * | 2020-09-24 | 2020-12-22 | 深圳市松柏实业发展有限公司 | Removing liquid for nickel-phosphorus coating, preparation method and removing method for nickel-phosphorus coating |
| CN113957442A (en) * | 2021-02-01 | 2022-01-21 | 江苏悦锌达新材料有限公司 | Nickel removing liquid medicine for nickel electroplating anti-corrosion layer, preparation method and chemical nickel removing process |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3540887B2 (en) | 2004-07-07 |
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