JP3146757B2 - Replacement gold plating solution - Google Patents
Replacement gold plating solutionInfo
- Publication number
- JP3146757B2 JP3146757B2 JP12399693A JP12399693A JP3146757B2 JP 3146757 B2 JP3146757 B2 JP 3146757B2 JP 12399693 A JP12399693 A JP 12399693A JP 12399693 A JP12399693 A JP 12399693A JP 3146757 B2 JP3146757 B2 JP 3146757B2
- Authority
- JP
- Japan
- Prior art keywords
- salts
- acid
- plating solution
- mol
- gold
- 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.)
- Expired - Lifetime
Links
- 238000007747 plating Methods 0.000 title claims description 57
- 239000010931 gold Substances 0.000 title claims description 35
- 229910052737 gold Inorganic materials 0.000 title claims description 35
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 33
- 150000003839 salts Chemical class 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000008139 complexing agent Substances 0.000 claims description 13
- 238000006073 displacement reaction Methods 0.000 claims description 9
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 claims description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical class OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical class OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 150000001735 carboxylic acids Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical class CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical class OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 claims description 2
- 229940018557 citraconic acid Drugs 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 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 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical class FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- -1 cyanide compound Chemical class 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 150000002343 gold Chemical class 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- KRZKNIQKJHKHPL-UHFFFAOYSA-J tripotassium;gold(1+);disulfite Chemical compound [K+].[K+].[K+].[Au+].[O-]S([O-])=O.[O-]S([O-])=O KRZKNIQKJHKHPL-UHFFFAOYSA-J 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZRBROGSAUIUIJE-UHFFFAOYSA-N azanium;azane;chloride Chemical compound N.[NH4+].[Cl-] ZRBROGSAUIUIJE-UHFFFAOYSA-N 0.000 description 1
- GABPAXJCPQEORA-UHFFFAOYSA-K azanium;gold(3+);disulfite Chemical compound [NH4+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O GABPAXJCPQEORA-UHFFFAOYSA-K 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 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
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- NRTDAKURTMLAFN-UHFFFAOYSA-N potassium;gold(3+);tetracyanide Chemical compound [K+].[Au+3].N#[C-].N#[C-].N#[C-].N#[C-] NRTDAKURTMLAFN-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Chemically Coating (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、置換金めっき液に関す
る。The present invention relates to a displacement gold plating solution.
【０００２】[0002]
【従来の技術】金めっきは、従来、装飾用や電子部品の
電気的接続部の接触抵抗を小さくするために多く用いら
れている。このような金めっきに用いるめっき液は、下
地が連続して導電性を有する材料の場合、電解めっきを
用いるが、電子部品、特に配線板や半導体装置のような
場合には、孤立した導体部分にめっきしなければならな
いことが多く、無電解めっきが用いられている。2. Description of the Related Art Conventionally, gold plating is widely used for decorative purposes or for reducing the contact resistance of electrical connection portions of electronic components. As a plating solution used for such gold plating, electrolytic plating is used when the base material is a material having continuous conductivity, but in the case of electronic components, particularly wiring boards and semiconductor devices, isolated conductive portions are used. In many cases, electroless plating is used.
【０００３】このような無電解金めっきを行うために、
下地金属と置換して金を析出させる置換金めっき液とし
ては、従来、シアン化物が用いられている。このような
例として、日本プレーティング協会編、昭和５９年９月
槇書店発行の「実用めっき（Ｉ）」には、シアン化金カ
リウム、塩化ニッケル、塩化コバルト、エチレンジアミ
ン四酢酸２ナトリウム、トリエタノールアミン、塩化ア
ンモニウム−アンモニア緩衝剤を含む置換金めっき液
を、ｐＨ６または９、液温９５℃で使用することが開示
され、日本プレーティング協会編、昭和５９年９月槇書
店発行の「実用めっき（III）」には、シアン化金ナト
リウム、シアン化ナトリウム、ソーダ灰を含む金めっき
液が開示されている。In order to perform such electroless gold plating,
Conventionally, cyanide has been used as a replacement gold plating solution that precipitates gold by replacing the underlying metal. For example, “Practical Plating (I)” published by Maki Shoten in September 1984, edited by the Japan Plating Association includes gold potassium cyanide, nickel chloride, cobalt chloride, disodium ethylenediaminetetraacetate, triethanol It was disclosed that a substituted gold plating solution containing an amine and an ammonium chloride-ammonia buffer was used at a pH of 6 or 9 and a liquid temperature of 95 ° C., and was published by Maki Shoten in September 1984, edited by the Japan Plating Association. (III) "discloses a gold plating solution containing sodium gold cyanide, sodium cyanide, and soda ash.
【０００４】また、置換金めっき液として、シアンを用
いないものとしては、特開平４−３１４８７０号公報
に、非シアン金源、亜硫酸塩、及びポリアミンとアミノ
カルボン酸を含む金属錯化剤を含むものが開示されてお
り、このポリアミンは、析出した金めっきの外観を向上
するために用いられている。Japanese Patent Application Laid-Open No. 4-314870 discloses a non-cyan gold-substituted solution containing a non-cyanide gold source, a sulfite, and a metal complexing agent containing a polyamine and an aminocarboxylic acid. The polyamine is used to improve the appearance of the deposited gold plating.
【０００５】さらにまた、還元剤を含み、その還元作用
によって被めっき体に金を析出させる還元金めっき液も
知られている。このようなものとして、還元剤にチオ尿
素を用いるものが特開昭６２−２７０７７９号公報、特
開昭６３−７９９７６号公報、特開平２−１０７７８０
号公報及び特開平４−３２５７５号公報に開示され、還
元剤にヒドラジン及びその化合物を用いるものが特開平
３−２１５６７７号公報や特開平４−３１４８７１号公
報に開示され、還元剤に水素化ホウ素化合物、次亜リン
酸、ホルマリン等を用いるものが特開昭６３−７９９７
６号公報、特開平２−１０７７８０号公報、あるいは特
開平１−１２５８９１号公報に開示されている。これら
のうち、特開昭６２−２７０７７９号公報、特開昭６３
−７９９７６号公報、特開平２−１０７７８０号公報、
特開平３−２１５６７７号公報、及び特開平４−３１４
８７１号公報には、金の錯化剤としてチオ硫酸を使用す
ることが開示されている。Further, a reduced gold plating solution which contains a reducing agent and deposits gold on a body to be plated by its reducing action is also known. As such materials, those using thiourea as a reducing agent are disclosed in JP-A-62-270779, JP-A-63-79976, and JP-A-2-107780.
And JP-A-4-32575, and those using hydrazine and its compound as a reducing agent are disclosed in JP-A-3-215677 and JP-A-4-314871, and borohydride is used as a reducing agent. Compounds using compounds, hypophosphorous acid, formalin, etc. are disclosed in JP-A-63-7997.
No. 6, JP-A-2-107780, and JP-A-1-125891. Of these, JP-A-62-270779 and JP-A-63-270779
-79976, JP-A-2-107780,
JP-A-3-215677 and JP-A-4-314
No. 871 discloses the use of thiosulfuric acid as a complexing agent for gold.
【０００６】[0006]
【発明が解決しようとする課題】ところで、置換金めっ
きにおいてシアン化合物を用いるものは、シアン化合物
が青酸カリの名称でも知られているとおり、微量でも毒
性の高いものであって、作業や保存に注意を払わねばな
らず、作業環境としても好ましいものではない。In the case where a cyanide compound is used in displacement gold plating, the cyanide is highly toxic even in a very small amount, as is known by the name of potassium cyanide. Must be paid, which is not preferable as a working environment.
【０００７】また、従来の置換金めっきを行うものであ
ってシアンを使用しないものは、めっき液中の金以外の
金属、例えば銅や鉄等をブロックする力が弱く、液の安
定性が低く、また、析出しためっきと下地金属であるニ
ッケルとの密着力が低い。[0007] In addition, the conventional plating method which uses substitutional gold plating and does not use cyan has a weak ability to block metals other than gold in the plating solution, for example, copper and iron, and has low stability of the solution. Also, the adhesion between the deposited plating and nickel as the base metal is low.
【０００８】さらにまた、従来の還元金めっきは、還元
剤との反応を、被めっき体の存在下においてのみ行わせ
ようとするために、液の安定剤を用いたり、液の組成比
を調節しなければならない。Further, in the conventional reduced gold plating, a liquid stabilizer is used or the composition ratio of the liquid is adjusted so that the reaction with the reducing agent is performed only in the presence of the object to be plated. Must.
【０００９】本発明は、シアン化合物を用いず毒性が低
く、かつ従来のシアン系置換金めっきと同等の皮膜特性
を有する非シアン置換金めっき液を提供することを目的
とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-cyanide-substituted gold plating solution having low toxicity without using a cyanide compound and having the same film properties as conventional cyan-based substitutional gold plating.
【００１０】[0010]
【課題を解決するための手段】本発明の置換金めっき液
は、非シアン金源、亜硫酸塩、及び金属錯化剤としてカ
ルボン酸又はその塩類を含み、不純物として、アンモニ
ウムイオン濃度が０．０２モル／ｌ以下、塩素イオン濃
度が０．３モル／ｌ以下、硫酸イオン濃度が０．３モル
／ｌ以下、臭素イオン濃度が０．０３モル／ｌ以下、ま
たはヨウ素イオン濃度が０．００６モル／ｌ以下である
ことを特徴とする。The substituted gold plating solution of the present invention contains a non-cyanide gold source, a sulfite, and carboxylic acid or a salt thereof as a metal complexing agent , and contains ammonium ion as an impurity. Concentration is 0.02 mol / l or less, chloride ion concentration is 0.3 mol / l or less, sulfate ion concentration is 0.3 mol / l or less, bromine ion concentration is 0.03 mol / l or less, or iodine ion concentration Is 0.006 mol / l or less.
【００１１】本発明に用いる非シアン金源としては、亜
硫酸金ナトリウム、亜硫酸金カリウム、亜硫酸金アンモ
ニウム、塩化金酸、塩化金酸ナトリウム、塩化金酸カリ
ウム、ヨウ化金酸ナトリウム、臭化金酸カリウム等のシ
アン化合物を使用しない金化合物を１種類以上使用する
ことができる。この非シアン金源の濃度は、０．５ｇ／
ｌ以上含むことが好ましく、１〜１０ｇ／ｌの範囲がさ
らに好ましい。濃度が０．５ｇ／ｌより低いと、置換反
応速度が低下し、１０ｇ／ｌを越えると、経済的でない
他、アンモニウムイオン、塩素イオン、臭素イオン、ヨ
ウ素イオン等不純物が増加し、後に述べるように、めっ
き液としての特性を低下させる。The non-cyanide gold source used in the present invention includes gold sodium sulfite, potassium gold sulfite, gold ammonium sulfite, chloroauric acid, sodium chloroaurate, potassium chloroaurate, sodium iodoaurate, and bromideaurate. One or more gold compounds that do not use a cyanide compound such as potassium can be used. The concentration of this non-cyanide gold source is 0.5 g /
and preferably 1 to 10 g / l. When the concentration is lower than 0.5 g / l, the substitution reaction rate is decreased. When the concentration is higher than 10 g / l, it is not economical, and impurities such as ammonium ion, chlorine ion, bromine ion and iodine ion increase, as described later. In addition, the characteristics as a plating solution are deteriorated.
【００１２】なかでも、上記不純物を含まない亜硫酸金
ナトリウムや亜硫酸金カリウムを用いることが好まし
く、他の金化合物を用いるときには、不純物として、ア
ンモニウムイオン濃度が０．０２モル／ｌ以下、塩素イ
オン濃度が０．３モル／ｌ以下、臭素イオン濃度が０．
０３モル／ｌ以下、またはヨウ素イオン濃度が０．００
６モル／ｌ以下となるようにめっき液を調整しなければ
ならない。アンモニウムイオン濃度が０．０２モル／
ｌ、塩素イオン濃度が０．３モル／ｌ、硫酸イオン濃度
が０．３モル／ｌ、臭素イオン濃度が０．０３モル／
ｌ、またはヨウ素イオン濃度が０．００６モル／ｌを越
えると、めっき液が不安定になったり、自己分解を起こ
すことがあり、下地ニッケルとの密着力の低下やめっき
皮膜の外観が悪化することもある。これらの不純物イオ
ンは、めっき液の他の成分によるものもあり、非シアン
金源に使用する組成と合わせて、ここに示した範囲を越
えないように調整することが好ましい。以下に他の組成
について述べるが、他の組成についてもこの不純物イオ
ンを含まないようにすることが好ましい。Above all, it is preferable to use sodium gold sulfite or potassium gold sulfite which do not contain the above impurities. When other gold compounds are used, the ammonium ion concentration is 0.02 mol / l or less and the chlorine ion concentration Is 0.3 mol / l or less, and the bromine ion concentration is 0.1 mol / l.
03 mol / l or less, or an iodine ion concentration of 0.00
The plating solution must be adjusted so as to be 6 mol / l or less. Ammonium ion concentration of 0.02 mol /
1, the chloride ion concentration is 0.3 mol / l, the sulfate ion concentration is 0.3 mol / l, and the bromine ion concentration is 0.03 mol / l.
If the l or iodine ion concentration exceeds 0.006 mol / l, the plating solution may become unstable or self-decompose, and the adhesion to the base nickel may be reduced and the appearance of the plating film may be deteriorated. Sometimes. These impurity ions may be due to other components of the plating solution, and are preferably adjusted so as not to exceed the range shown here, in combination with the composition used for the non-cyanide gold source. Other compositions will be described below, but it is preferable that the other compositions do not include the impurity ions.
【００１３】金属錯化剤としてのカルボン酸又はその塩
類としては、マロン酸とその塩類、シュウ酸とその塩
類、グルタル酸とその塩類、コハク酸とその塩類、マレ
イン酸とその塩類、シトラコン酸とその塩類、イタコン
酸とその塩類、プロピオン酸とその塩類、ギ酸とその塩
類、酢酸とその塩類から選択されたものを用いることが
できる。この金属錯化剤としてのカルボン酸又はその塩
類の濃度は、０．５ｇ／ｌ〜１００ｇ／ｌの範囲である
ことが好ましい。０．５ｇ／ｌ未満では、めっきの光沢
がなくなり、下地金属のニッケルやコバルトとの密着力
が低下することもある。１００ｇ／ｌを越えると、金光
沢を失い茶褐色となり好ましくない。Carboxylic acid or a salt thereof as a metal complexing agent
The kind, salts of malonic acid and its, salts of oxalic acid and its, salts of glutaric acid and its, salts and its succinate, salts of and its maleic acid, salts of citraconic acid and its, and its itaconate possible salts, salts and its propionic acid, salts of and its formic acid, the use of those selected from salts of acetic acid and its. Carboxylic acid or its salt as the metal complexing agent
Preferably , the concentration of the class is in the range from 0.5 g / l to 100 g / l. If it is less than 0.5 g / l, the luster of the plating is lost, and the adhesion to the underlying metal, nickel or cobalt, may be reduced. If it exceeds 100 g / l, it loses gold luster and becomes brownish, which is not preferable.
【００１４】亜硫酸塩の濃度は、７ｇ／ｌ〜１５０ｇ／
ｌの範囲であることが好ましい。７ｇ／ｌ未満である
と、めっき液の安定性が失われ、１５０ｇ／ｌを越える
と、置換反応が著しく抑制され、しかも経済的でなく好
ましくない。The concentration of the sulfite is 7 g / l to 150 g / l
It is preferably in the range of l. If it is less than 7 g / l, the stability of the plating solution is lost, and if it exceeds 150 g / l, the substitution reaction is remarkably suppressed, and it is not economical and not preferable.
【００１５】本発明の置換金めっき液は、ｐＨが、５〜
１２の範囲であることが好ましく、さらには６〜１１の
範囲が好ましい。５未満であると、亜硫酸が酸である水
素イオンと反応して有毒な亜硫酸ガスを発生し、１２を
越えると、金は析出するが、めっきレジストを使用した
ときに、レジストがめっき液に溶解しレジストとして使
用できなくなり好ましくない。ｐＨを調整するために各
種酸やアルカリを用いることができるが、上記不純物を
増加しないことが好ましい。例えば、アンモニウム塩を
用いるよりナトリウム塩やカリウム塩を使用することが
好ましい。The displacement gold plating solution of the present invention has a pH of 5 to 5.
It is preferably in the range of 12, more preferably in the range of 6 to 11. If it is less than 5, sulfurous acid reacts with hydrogen ions, which are acids, to generate toxic sulfurous acid gas. If it exceeds 12, gold precipitates, but when the plating resist is used, the resist dissolves in the plating solution. It is not preferable because it cannot be used as a resist. Various acids and alkalis can be used to adjust the pH, but it is preferable not to increase the impurities. For example, it is preferable to use a sodium salt or a potassium salt rather than using an ammonium salt.
【００１６】本発明の置換金めっき液の使用温度は、３
０〜９５℃が好ましく、めっきを行う下地金属は、ニッ
ケルやコバルトが好ましい。The working temperature of the displacement gold plating solution of the present invention is 3
The temperature is preferably 0 to 95 ° C., and nickel or cobalt is preferably used as a base metal for plating.
【００１７】[0017]
【作用】本発明は、発明者らが鋭意検討の結果、主成分
として、非シアン金源、亜硫酸塩、金属錯化剤としてカ
ルボン酸又はその塩類を用いたときに、アンモニウムイ
オン濃度が０．０２モル／ｌ以下、塩素イオン濃度が
０．３モル／ｌ以下、硫酸イオン濃度が０．３モル／ｌ
以下、臭素イオン濃度が０．０３モル／ｌ以下、または
ヨウ素イオン濃度が０．００６モル／ｌ以下であれば、
毒性を低くした上で、従来のシアン化合物を用いた金め
っき液と同等のめっき特性を得ることができるという知
見を得てなされたものである。According to the present invention, as a result of intensive studies, the present inventors have found that when non-cyanide gold source, sulfite, and carboxylic acid or its salts are used as metal complexing agents , Ion concentration of 0.02 mol / l or less, chloride ion concentration of 0.3 mol / l or less, sulfate ion concentration of 0.3 mol / l
Hereinafter, if the bromine ion concentration is 0.03 mol / l or less, or the iodine ion concentration is 0.006 mol / l or less,
It has been made based on the finding that it is possible to obtain plating properties equivalent to those of a conventional gold plating solution using a cyanide compound while reducing toxicity.
【００１８】[0018]
【実施例】ガラス布−エポキシ樹脂銅張り積層板である
ＭＣＬ−Ｅ−６７（日立化成工業株式会社製、商品名）
の回路とならない不要な銅箔の箇所をエッチング除去
し、水洗して、配線パターンを形成し、過硫酸アンモニ
ウム２００ｇ／ｌの水溶液に９０秒間浸漬して配線パタ
ーン表面を粗化し、水洗し、１０％の硫酸に６０秒浸漬
し、水洗し、無電解ニッケルめっき用触媒であるメルプ
レートアクチベータ３５０（メルテックス社製、商品
名）に５分間浸漬して配線パターン表面に触媒を付与
し、水洗し、無電解ニッケルめっきであるブルーシュー
マー（日本カニゼン株式会社製、商品名）に８５℃で３
０分間浸漬し、配線パターン表面にニッケルめっきを行
い、水洗した後、表１の組成と条件により置換めっきし
た。また、表に記載していない条件は、液温８５℃、浸
漬時間３０分間、ｐＨを７．０となるように、水酸化ナ
トリウムあるいは塩酸を用いて調整した。めっき面積は
５ｄｍ2／ｌを１サイクルとして、３０ｄｍ2／ｌまで連
続的にめっきして評価した。その結果を表１に示す。[Example] Glass cloth-epoxy resin copper clad laminate MCL-E-67 (trade name, manufactured by Hitachi Chemical Co., Ltd.)
Unnecessary portions of the copper foil that do not form a circuit are removed by etching, washed with water to form a wiring pattern, immersed in an aqueous solution of 200 g / l ammonium persulfate for 90 seconds to roughen the surface of the wiring pattern, washed with water, and washed with 10% Immersed in sulfuric acid for 60 seconds, washed with water, immersed in Melplate Activator 350 (manufactured by Meltex Corporation, trade name), which is a catalyst for electroless nickel plating, for 5 minutes to apply the catalyst to the wiring pattern surface, and washed with water, 3 at 85 ° C on Blue Schumer (product name, manufactured by Nippon Kanigen Co., Ltd.)
After immersion for 0 minutes, the surface of the wiring pattern was plated with nickel, washed with water, and then subjected to displacement plating according to the composition and conditions shown in Table 1. Conditions not described in the table were adjusted using sodium hydroxide or hydrochloric acid so that the solution temperature was 85 ° C., the immersion time was 30 minutes, and the pH was 7.0. Plating area as one cycle 5 dm 2 / l, was evaluated by continuously plating to 30dm 2 / l. Table 1 shows the results.
【００１９】[0019]
【表１】 [Table 1]
【００２０】この表からも分かるように、本発明の非シ
アン金源、亜硫酸塩、及び金属錯化剤としてカルボン酸
又はその塩類を用いたものは、めっきの外観、密着力及
びめっき液の安定性が共に優れている。これに対して、
比較例１では、金属錯化剤としてカルボン酸又はその塩
類を用いていないためにめっきの外観が悪い。この理由
は、ＥＳＣＡによって詳細に分析した結果、金めっき皮
膜に、金の置換反応によって発生する銅やニッケルが取
り込まれており、そのために緻密な金の皮膜が形成され
ていないからである。また、比較例の２〜６は、本発明
と同じ構成ではあるが、さらに、不純物であるアンモニ
ウムイオン、塩素イオン、硫酸イオン、臭素イオン、ま
たはヨウ素イオンが特定の値以上に含まれたものであ
り、めっき外観を改善する金属錯化剤の効果を抑制し、
外観が悪化する。さらにまた、比較例７は、シアンを用
いない金めっき液の従来例に使用されている金錯化剤と
してのチオ硫酸を、本発明のカルボン酸類に代えて用い
たものであるが、下地ニッケルとの密着力が低く、プリ
ント配線板等に使用する場合に充分な特性でないことが
分かる。[0020] As can be seen from the table, non-cyanide gold source, sulfites, and carboxylic acids as metal complexing agent of the present invention
Alternatively , those using salts thereof are excellent in plating appearance, adhesion and plating solution stability. On the contrary,
In Comparative Example 1, a carboxylic acid or a salt thereof was used as a metal complexing agent.
The appearance of the plating is poor because no metal is used. The reason for this is that, as a result of detailed analysis by ESCA, copper and nickel generated by the substitution reaction of gold are taken into the gold plating film, and therefore, a dense gold film is not formed. Further, Comparative Examples 2 to 6 have the same configuration as the present invention, but further contain ammonium ions, chloride ions, sulfate ions, bromine ions, or iodine ions, which are impurities, at a specific value or more. Yes, suppress the effect of metal complexing agent to improve plating appearance,
The appearance deteriorates. Furthermore, in Comparative Example 7, thiosulfuric acid as a gold complexing agent used in a conventional example of a gold plating solution not using cyan was used in place of the carboxylic acids of the present invention. It is understood that the adhesiveness is low and the characteristics are not sufficient when used for a printed wiring board or the like.
【００２１】[0021]
【発明の効果】以上に説明したように、本発明によっ
て、毒性が低く、かつ、シアンを用いた従来の置換金め
っきと同じようにめっき液の安定性、めっき外観、及び
下地金属との密着力等めっき皮膜特性に優れた非シアン
金めっき液を提供することができる。As described above, according to the present invention, the toxicity is low, and the stability of plating solution, plating appearance, and adhesion to the underlying metal are low as in the case of conventional displacement gold plating using cyan. A non-cyanide gold plating solution having excellent plating film properties such as force can be provided.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平６−330333（ＪＰ，Ａ) 特開 平６−228761（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C23C 18/00 - 18/54 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-330333 (JP, A) JP-A-6-228761 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C23C 18/00-18/54
Claims (5)
としてカルボン酸又はその塩類を含み、不純物として、
アンモニウムイオン濃度が０．０２モル／ｌ以下、塩素
イオン濃度が０．３モル／ｌ以下、硫酸イオン濃度が
０．３モル／ｌ以下、臭素イオン濃度が０．０３モル／
ｌ以下、またはヨウ素イオン濃度が０．００６モル／ｌ
以下であることを特徴とする置換金めっき液。1. A non-cyanide gold source, a sulfite, and a metal complexing agent.
As a carboxylic acid or a salt thereof, as an impurity,
The ammonium ion concentration is 0.02 mol / l or less, the chloride ion concentration is 0.3 mol / l or less, the sulfate ion concentration is 0.3 mol / l or less, and the bromine ion concentration is 0.03 mol / l.
l or less, or the iodine ion concentration is 0.006 mol / l
A displacement gold plating solution characterized by the following.
類が、マロン酸とその塩類、シュウ酸とその塩類、グル
タル酸とその塩類、コハク酸とその塩類、マレイン酸と
その塩類、シトラコン酸とその塩類、イタコン酸とその
塩類、プロピオン酸とその塩類、ギ酸とその塩類、酢酸
とその塩類から選択されたものであることを特徴とする
請求項１に記載の置換金めっき液。2. A carboxylic acid or a salt thereof as a metal complexing agent
S is, salts of malonic acid and its, salts of oxalic acid and its, salts of glutaric acid and its, salts and its succinate, and maleic acid
Their salts, salts of citraconic acid and its, salts of itaconic acid and its, salts and its propionic acid, salts of and its formic acid, acetic acid
Displacement gold plating solution according to claim 1, characterized in that the salts of and its those chosen.
ｌの範囲であることを特徴とする請求項１または２に記
載の置換金めっき液。3. A sulfite having a concentration of 7 g / l to 150 g / l.
The displacement gold plating solution according to claim 1 or 2, wherein the value is in the range of l.
類の濃度が、０．５ｇ／ｌ〜１００ｇ／ｌの範囲である
ことを特徴とする請求項１〜３のうちいずれかに記載の
置換金めっき液。4. A carboxylic acid or a salt thereof as a metal complexing agent
The replacement gold plating solution according to any one of claims 1 to 3 , wherein the concentration of the compound is in the range of 0.5 g / l to 100 g / l.
とする請求項１〜４のうちいずれかに記載の置換金めっ
き液。5. The replacement gold plating solution according to claim 1, wherein the pH is in the range of 5 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12399693A JP3146757B2 (en) | 1993-05-26 | 1993-05-26 | Replacement gold plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12399693A JP3146757B2 (en) | 1993-05-26 | 1993-05-26 | Replacement gold plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06330334A JPH06330334A (en) | 1994-11-29 |
| JP3146757B2 true JP3146757B2 (en) | 2001-03-19 |
Family
ID=14874462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12399693A Expired - Lifetime JP3146757B2 (en) | 1993-05-26 | 1993-05-26 | Replacement gold plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3146757B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101230651B1 (en) * | 2005-06-16 | 2013-02-06 | 메타로 테쿠노로지 쟈판 가부시키가이샤 | Electroless gold plating liquid |
-
1993
- 1993-05-26 JP JP12399693A patent/JP3146757B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06330334A (en) | 1994-11-29 |
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