JP2019214747A - Non-cyanide gold plating electrolytic solution - Google Patents
Non-cyanide gold plating electrolytic solution Download PDFInfo
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- JP2019214747A JP2019214747A JP2018111118A JP2018111118A JP2019214747A JP 2019214747 A JP2019214747 A JP 2019214747A JP 2018111118 A JP2018111118 A JP 2018111118A JP 2018111118 A JP2018111118 A JP 2018111118A JP 2019214747 A JP2019214747 A JP 2019214747A
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- gold plating
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- cyanide
- plating solution
- heat treatment
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- 238000007747 plating Methods 0.000 title claims abstract description 156
- 239000010931 gold Substances 0.000 title claims abstract description 150
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 150
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 239000008151 electrolyte solution Substances 0.000 title abstract 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 cyanide compound Chemical class 0.000 claims abstract description 49
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 33
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 235000002639 sodium chloride Nutrition 0.000 claims description 20
- 235000010265 sodium sulphite Nutrition 0.000 claims description 13
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 150000007524 organic acids Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 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 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 50
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 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 12
- 229910000531 Co alloy Inorganic materials 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 9
- SFOSJWNBROHOFJ-UHFFFAOYSA-N cobalt gold Chemical compound [Co].[Au] SFOSJWNBROHOFJ-UHFFFAOYSA-N 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 6
- 235000003704 aspartic acid Nutrition 0.000 description 6
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 6
- 239000004475 Arginine Substances 0.000 description 5
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 4
- 235000013922 glutamic acid Nutrition 0.000 description 4
- 239000004220 glutamic acid Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000002343 gold Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 2
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003353 gold alloy Substances 0.000 description 2
- 229910000457 iridium oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 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 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000009697 arginine Nutrition 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
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- RRDWZGMHSCBIGX-UHFFFAOYSA-J potassium;gold(3+);disulfite Chemical compound [K+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O RRDWZGMHSCBIGX-UHFFFAOYSA-J 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
本発明は、シアン化合物を含有しないノンシアン系電解金めっき液に関し、特に、硬質金めっき皮膜を形成できる、ノンシアン系電解金めっき液に関する。 The present invention relates to a non-cyanide-based electrolytic gold plating solution containing no cyanide, and more particularly to a non-cyanide-based electrolytic gold plating solution capable of forming a hard gold plating film.
耐腐食性に優れ高い電気伝導率を有する金めっき皮膜は、装飾分野のみならず、電子部品の接点材料や配線材料として電子工業分野においても広く使用されている。一般に、金めっき皮膜はその硬さにより、ビッカース硬さ（ＨＶ）１３０以上の硬質皮膜と、ＨＶ５０〜１００程度の軟質皮膜の２種類に分けられ、耐摩耗性が要求されるコネクタやプリント配線板の接点などには硬質金めっき皮膜が用いられる。 BACKGROUND ART A gold plating film having excellent corrosion resistance and high electric conductivity is widely used not only in the field of decoration but also in the field of electronic industry as a contact material and a wiring material for electronic components. Generally, gold plating films are classified into two types depending on their hardness: a hard film having a Vickers hardness (HV) of 130 or more and a soft film having a HV of about 50 to 100, and connectors and printed wiring boards requiring wear resistance. A hard gold plating film is used for the contact and the like.
従来、硬質金めっき皮膜には、主にコバルトやニッケルを含むシアン系金めっき液で電解めっきした、金−コバルト合金めっき皮膜や金−ニッケル合金めっき皮膜が用いられている。しかし、これらの合金めっき皮膜では、はんだリフロー工程などの熱処理により、合金めっき皮膜中のコバルトやニッケルが酸化され、表面変色や接触抵抗の増加が生じることが問題となっている。 Conventionally, as a hard gold plating film, a gold-cobalt alloy plating film or a gold-nickel alloy plating film electrolytically plated with a cyan gold plating solution containing mainly cobalt and nickel has been used. However, in these alloy plating films, heat treatment such as a solder reflow process oxidizes cobalt and nickel in the alloy plating film, causing a problem of surface discoloration and an increase in contact resistance.
金以外の金属を含有せず、電解めっきで硬さがＨＶ１６０に達する純金めっき皮膜を形成できるシアン系金めっき液も知られている。純金めっき皮膜であれば、酸化による表面変色や接触抵抗の増加は生じ難い。しかし、純金めっき皮膜は、通常熱処理によって硬度が低下してしまう。これは、純金めっき皮膜では、金の結晶粒が熱処理により大きく成長することが要因と考えられており、耐熱性に優れる硬質純金めっき皮膜を得ることは難しい。 There is also known a cyan gold plating solution which does not contain metals other than gold and can form a pure gold plating film whose hardness reaches HV160 by electrolytic plating. With a pure gold plating film, surface discoloration due to oxidation and an increase in contact resistance hardly occur. However, the hardness of the pure gold plating film is usually reduced by the heat treatment. This is considered to be due to the fact that gold crystal grains grow significantly by heat treatment in a pure gold plating film, and it is difficult to obtain a hard pure gold plating film having excellent heat resistance.
一方、近年シアン系金めっき液は毒性の高いシアン化合物を含むことから、作業上の安全性、環境負荷などが問題となっており、シアン化合物を含まないノンシアン系電解金めっき液が注目されている。例えば、特許文献１には電解めっきで硬質金めっき皮膜を形成できる、コバルト又はニッケルを含むノンシアン系合金めっき液が提案されている。しかし、一般に使用されているノンシアン系電解金めっき液は、主に軟質皮膜の形成に用いられているのが現状である。 On the other hand, in recent years, since cyanide-based gold plating solutions contain highly toxic cyanide compounds, work safety, environmental load, and the like have become problems, and non-cyanide-based electrolytic gold plating solutions that do not contain cyanide have been attracting attention. I have. For example, Patent Document 1 proposes a non-cyanide alloy plating solution containing cobalt or nickel, which can form a hard gold plating film by electrolytic plating. However, at present, non-cyanide electrolytic gold plating solutions generally used are mainly used for forming soft films.
本発明はこのような事情に鑑みてなされたものであり、シアン化合物を含有せず、耐熱性に優れた硬質金めっき皮膜を形成できる、ノンシアン系電解金めっき液を提供することを目的とする。 The present invention has been made in view of such circumstances, and has as its object to provide a non-cyanide-based electrolytic gold plating solution that does not contain a cyanide compound and can form a hard gold plating film having excellent heat resistance. .
（１）本発明のノンシアン系電解金めっき液は、金イオン供給源と、無機酸又は無機酸塩の少なくとも一方と、チオ尿素系化合物と、エチレンアミン化合物とを含有することを特徴とする。 (1) The non-cyanide electrolytic gold plating solution of the present invention is characterized by containing a gold ion supply source, at least one of an inorganic acid or an inorganic acid salt, a thiourea-based compound, and an ethyleneamine compound.
（２）（１）において、前記チオ尿素系化合物は、チオ尿素、メチルチオ尿素、及びエチレンチオ尿素から選択される少なくとも一つを含むことを特徴とする。 (2) In (1), the thiourea-based compound includes at least one selected from thiourea, methylthiourea, and ethylenethiourea.
（３）（１）又は（２）において、前記エチレンアミン化合物は、エチレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びポリエチレンイミンから選択される少なくとも一つを含むことを特徴とする。 (3) In the constitution (1) or (2), the ethyleneamine compound contains at least one selected from ethylenediamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine.
（４）（１）から（３）のいずれかにおいて、前記無機酸は、硫酸、塩酸、亜硫酸、リン酸、及びスルファミン酸から選択される少なくとも一つを含み、前記無機酸塩は、亜硫酸ナトリウム、亜硫酸カリウム、硫酸ナトリウム、硫酸カリウム、塩化ナトリウム、塩化カリウム、塩化アンモニウム、及びスルファミン酸アンモニウムから選択される少なくとも一つを含むことを特徴とする。 (4) In any one of (1) to (3), the inorganic acid includes at least one selected from sulfuric acid, hydrochloric acid, sulfurous acid, phosphoric acid, and sulfamic acid, and the inorganic acid salt is sodium sulfite. , Potassium sulfite, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, ammonium chloride, and ammonium sulfamate.
（５）（１）から（４）のいずれかにおいて、前記チオ尿素系化合物の含有量は１ｍｇ／Ｌ以上、１０００ｍｇ／Ｌ以下であり、前記エチレンアミン化合物の含有量は０．５ｇ／Ｌ以上、２００ｇ／Ｌ以下であることを特徴とする。 (5) In any one of (1) to (4), the content of the thiourea-based compound is 1 mg / L or more and 1000 mg / L or less, and the content of the ethyleneamine compound is 0.5 g / L or more. , 200 g / L or less.
（６）（１）から（５）のいずれかにおいて、有機酸又は有機酸塩の少なくとも一方を含有することを特徴とする。 (6) The method according to any one of (1) to (5), wherein at least one of an organic acid and an organic acid salt is contained.
本発明によれば、シアン化合物を含有せず、耐熱性に優れた硬質金めっき皮膜を形成できる、ノンシアン系電解金めっき液を提供することができる。 According to the present invention, it is possible to provide a non-cyanide electrolytic gold plating solution that does not contain a cyanide compound and can form a hard gold plating film having excellent heat resistance.
本発明者らは、シアンを含有しない水溶性金塩と、無機酸又は無機酸塩を含有するノンシアン系電解金めっき液に、チオ尿素系化合物とエチレンアミン化合物とを加えることにより、熱処理しても硬度が低下しない硬質金めっき皮膜を形成できることを見出し、さらなる検討の結果本発明を完成させるに至った。以下、本発明の実施形態の一例について詳細に説明するが、本発明はこれらに限定されるものではない。 The present inventors heat-treated by adding a thiourea-based compound and an ethyleneamine compound to a water-soluble gold salt containing no cyanide and a non-cyanide-based electrolytic gold plating solution containing an inorganic acid or an inorganic acid salt. It was also found that a hard gold plating film whose hardness did not decrease could be formed, and as a result of further studies, the present invention was completed. Hereinafter, an example of an embodiment of the present invention will be described in detail, but the present invention is not limited thereto.
実施形態のノンシアン系電解金めっき液（以下、「金めっき液」ということもある。）は、金イオンと、無機酸又は無機酸塩の少なくとも一方と、チオ尿素系化合物とエチレンアミン化合物とを含有する電解めっき用の金めっき液である。金めっき液がチオ尿素系化合物とエチレンアミン化合物とを含有することにより、熱処理後も硬さが維持できるＨＶ１３０以上の硬質金めっき皮膜が形成できる。また、形成された硬質金めっき皮膜は、金以外の金属を含有しないので、熱処理を行っても酸化による表面変色や接触抵抗の増加が生じ難い。 The non-cyanide-based electrolytic gold plating solution of the embodiment (hereinafter, also referred to as “gold plating solution”) includes a gold ion, at least one of an inorganic acid or an inorganic acid salt, a thiourea-based compound, and an ethyleneamine compound. It is a gold plating solution for electrolytic plating contained. When the gold plating solution contains a thiourea-based compound and an ethyleneamine compound, a hard gold plating film having an HV of 130 or more that can maintain hardness even after heat treatment can be formed. Moreover, since the formed hard gold plating film does not contain metals other than gold, even if heat treatment is performed, surface discoloration due to oxidation and an increase in contact resistance hardly occur.
金イオンを供給する金イオン供給源には、シアンを含有しない水溶性金塩を使用でき、例えば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、塩化金酸ナトリウム、塩化金酸カリウム、塩化金酸アンモニウムなどを用いることができる。金イオン供給源の量は、金めっき液中の金濃度が０．５ｇ／Ｌ〜４０ｇ／Ｌとなるよう調整することが好ましい。 As a gold ion source for supplying gold ions, a water-soluble gold salt containing no cyanide can be used. For example, sodium gold sulfite, gold potassium sulfite, gold ammonium sulfite, sodium chloroaurate, potassium chloroaurate, chloroauric acid Ammonium or the like can be used. It is preferable to adjust the amount of the gold ion supply source so that the gold concentration in the gold plating solution is 0.5 g / L to 40 g / L.
金めっき液が含有するチオ尿素系化合物には、例えばチオ尿素、メチルチオ尿素、及びエチレンチオ尿素の１種又は２種以上を用いることができる。金めっき液中のチオ尿素系化合物の含有量は、１ｍｇ／Ｌ以上、１０００ｍｇ／Ｌ以下の範囲が好ましく、３ｍｇ／Ｌ以上、２００ｍｇ／Ｌ以下の範囲がより好ましい。チオ尿素系化合物の含有量が少なすぎると効果が得られず、多すぎると液安定性が低下する。 As the thiourea-based compound contained in the gold plating solution, for example, one or more of thiourea, methylthiourea, and ethylenethiourea can be used. The content of the thiourea-based compound in the gold plating solution is preferably in the range of 1 mg / L or more and 1000 mg / L or less, more preferably 3 mg / L or more and 200 mg / L or less. If the content of the thiourea-based compound is too small, no effect can be obtained, and if it is too large, the liquid stability decreases.
エチレンアミン化合物には、例えばエチレンジアミン、トリエチレンテトラミン、テトラエチレンペンタミン、及びポリエチレンイミンの１種又は２種以上を用いることができる。エチレンアミン化合物の金めっき液中の含有量は、０．５ｇ／Ｌ以上、２００ｇ／Ｌ以下の範囲が好ましく、５ｇ／Ｌ以上、１００ｇ／Ｌ以下の範囲がより好ましい。エチレンアミン化合物の含有量が少なすぎると効果が得られず、多すぎると液安定性が低下する。 As the ethyleneamine compound, for example, one or more of ethylenediamine, triethylenetetramine, tetraethylenepentamine, and polyethyleneimine can be used. The content of the ethyleneamine compound in the gold plating solution is preferably in the range of 0.5 g / L to 200 g / L, and more preferably in the range of 5 g / L to 100 g / L. If the content of the ethyleneamine compound is too small, no effect is obtained, and if it is too large, the liquid stability decreases.
無機酸又は無機酸塩は特に限定されるものではなく、無機伝導塩として公知のものが利用可能である。このような無機酸には、例えば硫酸、塩酸、亜硫酸、リン酸、スルファミン酸などを、また無機酸塩には例えば亜硫酸ナトリウム、亜硫酸カリウム、硫酸ナトリウム、硫酸カリウム、塩化ナトリウム、塩化カリウム、塩化アンモニウム、スルファミン酸アンモニウムなどを挙げることができる。金めっき液中の無機酸及び無機酸塩の添加量は特に限定されないが、好ましくは１ｇ／Ｌ以上、２００ｇ／Ｌ以下、より好ましくは１０ｇ／Ｌ以上、１００ｇ／Ｌ以下である。 The inorganic acid or inorganic acid salt is not particularly limited, and any known inorganic conductive salt can be used. Such inorganic acids include, for example, sulfuric acid, hydrochloric acid, sulfurous acid, phosphoric acid, and sulfamic acid, and inorganic acid salts include, for example, sodium sulfite, potassium sulfite, sodium sulfate, potassium sulfate, sodium chloride, potassium chloride, and ammonium chloride. And ammonium sulfamate. The amount of the inorganic acid and the inorganic acid salt in the gold plating solution is not particularly limited, but is preferably 1 g / L or more and 200 g / L or less, more preferably 10 g / L or more and 100 g / L or less.
また、有機酸又は有機酸塩の少なくとも一方を添加してもよい。添加する有機酸、有機酸塩としては、例えばグルタミン酸、アスパラギン酸、アルギニンなどとこれらの塩が挙げられる。有機酸、有機酸塩の添加量は特に限定されないが、好ましくは１ｇ／Ｌ以上、２００ｇ／Ｌ以下、より好ましくは１０ｇ／Ｌ以上、１００ｇ／Ｌ以下である。 Further, at least one of an organic acid and an organic acid salt may be added. Examples of the organic acid and organic acid salt to be added include glutamic acid, aspartic acid, arginine and the like, and salts thereof. The amount of the organic acid or organic acid salt is not particularly limited, but is preferably 1 g / L or more and 200 g / L or less, more preferably 10 g / L or more and 100 g / L or less.
金めっき液のｐＨは硫酸、塩酸、水酸化ナトリウム、水酸化カリウム、アンモニアなどを添加して調整することが可能であり、ｐＨは６〜１１が好ましい。また、本発明のノンシアン系電解金めっき液は、必要に応じて他の成分を本発明の目的を損なわない範囲で添加することも可能である。例えば、めっき液中の不純物金属イオン対策として、キレート剤を適宜添加してもよい。界面活性剤、平滑化剤、酸化防止剤などを添加してもよい。 The pH of the gold plating solution can be adjusted by adding sulfuric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonia or the like, and the pH is preferably 6 to 11. Further, to the non-cyanide electrolytic gold plating solution of the present invention, if necessary, other components can be added within a range not to impair the object of the present invention. For example, a chelating agent may be appropriately added as a countermeasure against impurity metal ions in the plating solution. Surfactants, leveling agents, antioxidants and the like may be added.
以下、本発明の実施例であるノンシアン系電解金めっき液と、当該実施例を用いて電解めっきにより形成した金めっき皮膜の評価試験例を述べるが、本発明はこれらの実施例に限定されるものではない。
［実施例１］
金イオン供給源に亜硫酸金ナトリウム、チオ尿素系化合物に１−メチルチオ尿素、エチレンアミン化合物にトリエチレンテトラミン、無機酸塩に亜硫酸ナトリウム、有機酸にアルギニンを用い、下記の組成で実施例１のノンシアン系電解金めっき液を調製した。めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ９に調整した。なお、以下の実施例、比較例において、亜硫酸金ナトリウムの含有量（ｇ／Ｌ）は、金めっき液中の金の濃度に換算した値で示す。
実施例１の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の濃度）
・１−メチルチオ尿素 ８０ｍｇ／Ｌ
・トリエチレンテトラミン ３０ｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・アルギニン １０ｇ／Ｌ
Hereinafter, a non-cyanide-based electrolytic gold plating solution that is an example of the present invention and an evaluation test example of a gold plating film formed by electrolytic plating using the example will be described, but the present invention is limited to these examples. Not something.
[Example 1]
Using sodium gold sulfite as a source of gold ions, 1-methylthiourea as a thiourea-based compound, triethylenetetramine as an ethyleneamine compound, sodium sulfite as an inorganic acid salt, and arginine as an organic acid, the following composition of Example 1 was used. A system electrolytic gold plating solution was prepared. The pH of the plating solution was adjusted to pH 9 by adding sodium hydroxide and sulfuric acid. In the following Examples and Comparative Examples, the content (g / L) of sodium gold sulfite is indicated by a value converted to the concentration of gold in a gold plating solution.
Composition of gold plating solution of Example 1 Gold sodium sulfite 10 g / L (concentration of gold in gold plating solution)
-1-methylthiourea 80mg / L
・ Triethylenetetramine 30g / L
・ Sodium sulfite 40g / L
・ Arginine 10g / L
金めっき皮膜を評価するため、ノンシアン金ストライクめっきを施したＮｉ板上に、実施例１の金めっき液を用い、液温６０℃、陰極電流密度０．３Ａ/ｄｍ２の条件で、厚さ１０μｍの金めっき皮膜を形成した。金めっき液はスターラーを使用して攪拌し、陽極には酸化イリジウム系電極アノデック１００（日進化成株式会社製）を使用した。 In order to evaluate the gold plating film, the gold plating solution of Example 1 was used on a Ni plate subjected to non-cyanide gold strike plating, at a solution temperature of 60 ° C. and a cathode current density of 0.3 A / dm 2, and a thickness of 10 μm. Was formed. The gold plating solution was stirred using a stirrer, and an iridium oxide-based electrode Anodec 100 (manufactured by Nisshinsei Co., Ltd.) was used as the anode.
得られた金めっき皮膜は光沢外観を有し、ビッカース硬さ測定を行った結果、ＨＶ１７９の硬質皮膜であった。また、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。 The obtained gold plating film had a glossy appearance, and was measured for Vickers hardness. As a result, it was a HV179 hard film. The contact resistance (measuring load: 0.25 N) was 1 mΩ or less.
次に、金めっき皮膜の耐熱性を評価するため、大気下で、２５０℃、３０分、及び４００℃、３０分の熱処理をそれぞれ行い、ビッカース硬さと接触抵抗の変化を調べた。２５０℃の熱処理後の金めっき皮膜は、光沢外観を有し外観に変化は見られず、硬さはＨＶ１７８で熱処理前と同等であった。接触抵抗も１ｍΩ以下で熱処理前から変化は認められなかった。 Next, in order to evaluate the heat resistance of the gold plating film, heat treatment was performed in air at 250 ° C. for 30 minutes and at 400 ° C. for 30 minutes, respectively, and changes in Vickers hardness and contact resistance were examined. The gold plating film after the heat treatment at 250 ° C. had a glossy appearance and no change was observed in the appearance, and had a hardness of HV178 equivalent to that before the heat treatment. The contact resistance was 1 mΩ or less, and no change was observed before the heat treatment.
また、４００℃の熱処理後の金めっき皮膜も、光沢外観を有し外観に変化は見られず、硬さはＨＶ１７２で熱処理前と同等であった。接触抵抗も１ｍΩ以下で熱処理前と変化は認められない。４００℃の熱処理前後の金めっき皮膜表面を、走査電子顕微鏡（ＳＥＭ）で観察した結果を図１、２に示す。図１は熱処理前（As-depo）のＳＥＭ像であり、図２は大気下、４００℃、３０分の熱処理後のＳＥＭ像である。図１、２を比較しても金めっき皮膜表面には変化が認められず、４００℃の熱処理による影響が小さいことがわかる。 The gold plating film after the heat treatment at 400 ° C. also had a glossy appearance and no change was observed in the appearance, and had a hardness of HV172 equivalent to that before the heat treatment. The contact resistance was 1 mΩ or less, and no change was observed from before the heat treatment. FIGS. 1 and 2 show the results of observing the surface of the gold plating film before and after the heat treatment at 400 ° C. with a scanning electron microscope (SEM). FIG. 1 is an SEM image before heat treatment (As-depo), and FIG. 2 is an SEM image after heat treatment at 400 ° C. for 30 minutes in the atmosphere. 1 and 2, no change is recognized on the surface of the gold plating film, and it can be seen that the influence of the heat treatment at 400 ° C. is small.
［実施例２］
実施例１の有機酸をアルギニンからアスパラギン酸に換え、以下の組成で実施例２のノンシアン系電解金めっき液を調製した。めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ８に調整した。
実施例２の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の濃度）
・１−メチルチオ尿素 ５０ｍｇ／Ｌ
・トリエチレンテトラミン ３０ｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・アスパラギン酸 ４０ｇ／Ｌ
[Example 2]
The organic acid of Example 1 was changed from arginine to aspartic acid, and a non-cyanide electrolytic gold plating solution of Example 2 was prepared with the following composition. The pH of the plating solution was adjusted to pH 8 by adding sodium hydroxide and sulfuric acid.
Gold plating solution composition of Example 2 • Gold sodium sulfite 10 g / L (concentration of gold in gold plating solution)
・ 1-methylthiourea 50mg / L
・ Triethylenetetramine 30g / L
・ Sodium sulfite 40g / L
・ Aspartic acid 40g / L
ノンシアン金ストライクめっきを施したＮｉ板上に、実施例２の金めっき液を用い、液温６０℃、陰極電流密度０．４Ａ/ｄｍ２の条件で、実施例１と同じように厚さ１０μｍの金めっき皮膜を形成した。得られた金めっき皮膜は光沢外観を有し、ビッカース硬さ測定を行った結果、ＨＶ１７０の硬質皮膜であった。また、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。 Using a gold plating solution of Example 2 on a Ni plate having been subjected to non-cyanide gold strike plating, a thickness of 10 μm as in Example 1 at a solution temperature of 60 ° C. and a cathode current density of 0.4 A / dm 2. A gold plating film was formed. The obtained gold plating film had a glossy appearance, and was measured for Vickers hardness. As a result, it was a hard film of HV170. The contact resistance (measuring load: 0.25 N) was 1 mΩ or less.
この金めっき皮膜に、大気下、２５０℃、３０分の熱処理を行い、ビッカース硬さと接触抵抗の変化を調べた。結果、金めっき皮膜は熱処理後も外観は光沢外観を有し、硬さもＨＶ１６７で熱処理前と同等であった。接触抵抗も１ｍΩ以下で熱処理前から変化は認められない。 This gold plated film was subjected to a heat treatment at 250 ° C. for 30 minutes in the atmosphere, and changes in Vickers hardness and contact resistance were examined. As a result, the gold plating film had a glossy appearance even after the heat treatment, and the hardness was HV167, which was equivalent to that before the heat treatment. The contact resistance is 1 mΩ or less, and no change is observed before the heat treatment.
［実施例３］
チオ尿素系化合物にチオ尿素、エチレンアミン化合物にテトラエチレンペンタミンを用い、亜硫酸金ナトリウム、亜硫酸ナトリウム、グルタミン酸を下記の組成で含有する、実施例３のノンシアン系電解金めっき液を調製した。金めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ８に調整した。
実施例３の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の濃度）
・チオ尿素 ３０ｍｇ／Ｌ
・テトラエチレンペンタミン ２０ｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・グルタミン酸 ２０ｇ／Ｌ
[Example 3]
Using thiourea as the thiourea-based compound and tetraethylenepentamine as the ethyleneamine compound, a non-cyanide-based electrolytic gold plating solution of Example 3 containing sodium gold sulfite, sodium sulfite, and glutamic acid in the following composition was prepared. The pH of the gold plating solution was adjusted to pH 8 by adding sodium hydroxide and sulfuric acid.
Gold plating solution composition of Example 3 • Gold sodium sulfite 10 g / L (concentration of gold in gold plating solution)
・ Thiourea 30mg / L
・ Tetraethylenepentamine 20g / L
・ Sodium sulfite 40g / L
・ Glutamic acid 20g / L
ノンシアン金ストライクめっきを施したＮｉ板上に、実施例３の金めっき液を用い、液温６０℃、陰極電流密度０．３Ａ/ｄｍ２の条件で、実施例１と同じように厚さ１０μｍの金めっき皮膜を形成した。得られた金めっき皮膜は光沢外観を有し、ビッカース硬さ測定を行った結果、ＨＶ１６９の硬質皮膜であった。また、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。 Using a gold plating solution of Example 3 on a Ni plate having been subjected to non-cyanide gold strike plating, at a solution temperature of 60 ° C. and a cathode current density of 0.3 A / dm2, a thickness of 10 μm as in Example 1. A gold plating film was formed. The obtained gold plating film had a glossy appearance, and was measured for Vickers hardness. As a result, it was a hard film of HV169. The contact resistance (measuring load: 0.25 N) was 1 mΩ or less.
この金めっき皮膜に、大気下、４００℃、３０分の熱処理を行い、ビッカース硬さと接触抵抗の変化を調べた。結果、熱処理後も外観は光沢外観を有し、硬さはＨＶ１７６と熱処理前と同等であった。接触抵抗も１ｍΩ以下で熱処理前から変化は認められない。 This gold plating film was subjected to a heat treatment at 400 ° C. for 30 minutes in the atmosphere, and changes in Vickers hardness and contact resistance were examined. As a result, the appearance was glossy after the heat treatment, and the hardness was the same as that of the HV176 before the heat treatment. The contact resistance is 1 mΩ or less, and no change is observed before the heat treatment.
［実施例４］
チオ尿素系化合物にチオ尿素、エチレンアミン化合物にエチレンジアミンを用い、亜硫酸金ナトリウム、亜硫酸ナトリウム、アスパラギン酸を下記の組成で含有する、実施例４のノンシアン系電解金めっき液を調製した。金めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ８に調整した。
実施例４の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の濃度）
・チオ尿素 ４０ｍｇ／Ｌ
・エチレンジアミン ５０ｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・アスパラギン酸 ４０ｇ／Ｌ
[Example 4]
Using thiourea as the thiourea-based compound and ethylenediamine as the ethyleneamine compound, a non-cyanide-based electrolytic gold plating solution of Example 4 containing sodium gold sulfite, sodium sulfite, and aspartic acid in the following composition was prepared. The pH of the gold plating solution was adjusted to pH 8 by adding sodium hydroxide and sulfuric acid.
Gold plating solution composition of Example 4 • Gold sodium sulfite 10 g / L (concentration of gold in gold plating solution)
・ Thiourea 40mg / L
・ Ethylenediamine 50g / L
・ Sodium sulfite 40g / L
・ Aspartic acid 40g / L
ノンシアン金ストライクめっきを施したＮｉ板上に、実施例４の金めっき液を用い、液温５５℃、陰極電流密度０．４Ａ/ｄｍ２の条件で、実施例１と同じように厚さ１０μｍの金めっき皮膜を形成した。得られた金めっき皮膜は光沢外観を有し、ビッカース硬さ測定を行った結果、ＨＶ１６１の硬質皮膜であった。また、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。 On the Ni plate subjected to non-cyanide gold strike plating, using the gold plating solution of Example 4 at a solution temperature of 55 ° C. and a cathode current density of 0.4 A / dm 2, a thickness of 10 μm as in Example 1 was used. A gold plating film was formed. The obtained gold plating film had a glossy appearance, and was measured for Vickers hardness. As a result, it was a hard film of HV161. The contact resistance (measuring load: 0.25 N) was 1 mΩ or less.
この金めっき皮膜に、大気下、３５０℃、３０分の熱処理を行い、ビッカース硬さと接触抵抗の変化を調べた。結果、熱処理後も外観は光沢外観を有し、硬さはＨＶ１５６と熱処理前と同等であった。接触抵抗も１ｍΩ以下で熱処理前から変化は認められない。 This gold plated film was subjected to a heat treatment at 350 ° C. for 30 minutes in the atmosphere, and changes in Vickers hardness and contact resistance were examined. As a result, the appearance was glossy after the heat treatment, and the hardness was the same as that of the HV156 before the heat treatment. The contact resistance is 1 mΩ or less, and no change is observed before the heat treatment.
実施例１から４のノンシアン系電解金めっき液について、連続使用を想定してめっき液中に含まれる金量と同じ量の金をめっきで析出させ、減少した成分を補充する回数（ＭＴＯ：Metal Turn Over）を調べた。その結果、実施例１から４いずれも５ターンを超えて良好な金めっき皮膜を形成でき、めっき液の濁りなどを生じることもなかった。 Regarding the non-cyanide electrolytic gold plating solutions of Examples 1 to 4, assuming continuous use, the same amount of gold contained in the plating solution was deposited by plating, and the reduced component was replenished (MTO: Metal) Turn Over). As a result, in each of Examples 1 to 4, a good gold plating film could be formed over 5 turns, and the plating solution did not become turbid.
以上の結果から、実施例１から４のノンシアン系電解金めっき液では、電解めっきにより硬質金めっき皮膜を形成できることがわかる。形成された硬質金めっき皮膜は、熱処理を行っても硬さを維持でき、変色や接触抵抗の増加が起こらない、耐熱性に優れる硬質金めっき皮膜であることがわかる。また、実施例１から４のノンシアン系電解金めっき液は、５ターンを超えて良好な金めっき皮膜を形成でき、安定性に優れることがわかる。 From the above results, it can be seen that a hard gold plating film can be formed by electrolytic plating with the non-cyanide-based electrolytic gold plating solutions of Examples 1 to 4. It can be seen that the formed hard gold plating film is a hard gold plating film which can maintain hardness even after heat treatment, does not cause discoloration and increases contact resistance, and has excellent heat resistance. Further, it can be seen that the non-cyanide electrolytic gold plating solutions of Examples 1 to 4 can form a good gold plating film for more than 5 turns and have excellent stability.
比較のため、一般に用いられているコバルトを含むシアン系電解金めっき液と、チオ尿素系化合物又はエチレンアミン化合物を含有しないノンシアン系電解金めっき液をそれぞれ調製し、電解めっきにより得られた金めっき皮膜の評価を行った。
［比較例１］
比較例１として、シアン化金カリウム８ｇ／Ｌ（めっき液中の金の濃度に換算して）、硫酸コバルト１ｇ／Ｌ（めっき液中のコバルトの濃度に換算して）を含有するシアン系金コバルト合金めっき液を使用し、金ストライクめっきを施したＮｉ板上に、液温４０℃、陰極電流密度０．５Ａ／ｄｍ２の条件で、厚さ１０μｍの金−コバルト合金めっき皮膜を形成した。電解めっきは実施例１と同じように、スターラーで攪拌し陽極に酸化イリジウム系電極アノデック１００を使用して行った。得られた金−コバルト合金めっき皮膜は光沢外観を有し、ビッカース硬さ測定を行った結果、ＨＶ１５９の硬質皮膜であった。また、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。
For comparison, a commonly used cyan-based electrolytic gold plating solution containing cobalt and a non-cyanide-based electrolytic gold plating solution containing no thiourea-based compound or ethyleneamine compound were prepared, respectively, and the gold plating obtained by electrolytic plating was used. The coating was evaluated.
[Comparative Example 1]
As Comparative Example 1, cyan-based gold containing 8 g / L of potassium gold cyanide (in terms of the concentration of gold in the plating solution) and 1 g / L of cobalt sulfate (in terms of the concentration of cobalt in the plating solution) Using a cobalt alloy plating solution, a 10-μm-thick gold-cobalt alloy plating film was formed on a gold strike-plated Ni plate at a liquid temperature of 40 ° C. and a cathode current density of 0.5 A / dm 2. Electrolytic plating was performed by stirring with a stirrer and using an iridium oxide-based electrode Anodec 100 as the anode, as in Example 1. The obtained gold-cobalt alloy plating film had a glossy appearance, and was measured for Vickers hardness. As a result, it was a hard film of HV159. The contact resistance (measuring load: 0.25 N) was 1 mΩ or less.
得られた金−コバルト合金めっき皮膜を、大気下で、２５０℃、３０分、及び４００℃、３０分の熱処理をそれぞれ行い、ビッカース硬さと接触抵抗の変化を調べた。２５０℃の熱処理後の金−コバルト合金めっき皮膜では、硬さはＨＶ１６０と熱処理前と同等であり、接触抵抗は１ｍΩ以下で熱処理前と変わらなかった。しかし、皮膜外観は若干暗くなり光沢度の低下が認められた。 The obtained gold-cobalt alloy plating film was subjected to heat treatment at 250 ° C. for 30 minutes and 400 ° C. for 30 minutes in the air, respectively, and changes in Vickers hardness and contact resistance were examined. The hardness of the gold-cobalt alloy plating film after the heat treatment at 250 ° C. was equal to that of the HV160 before the heat treatment, and the contact resistance was 1 mΩ or less, which was the same as that before the heat treatment. However, the appearance of the film was slightly darkened, and a decrease in glossiness was observed.
４００℃の熱処理後の金−コバルト合金めっき皮膜は、硬さはＨＶ１５５と熱処理前と同等であった。しかし、皮膜外観は暗くなり光沢度が大きく低下した。また、接触抵抗も２０ｍΩ以上に劣化した。４００℃の熱処理前後の金−コバルト合金めっき皮膜表面を、ＳＥＭで観察した結果を図３、４に示す。図３は熱処理前（As-depo）のＳＥＭ像であり、図４は熱処理後のＳＥＭ像である。図３、４を比較すると、熱処理後の金−コバルト合金めっき皮膜表面には、白い斑点状の領域が現れており、熱処理によりコバルトが酸化し表面が変質していることがわかる。比較例１では、４００℃の熱処理後も硬さは維持されたが、２５０℃の熱処理で外観の光沢度の低下が認められ、４００℃の熱処理ではコバルトの酸化により接触抵抗が劣化した。 The hardness of the gold-cobalt alloy plating film after the heat treatment at 400 ° C. was equal to HV155 as before the heat treatment. However, the appearance of the film became dark and the glossiness was greatly reduced. Further, the contact resistance also deteriorated to 20 mΩ or more. FIGS. 3 and 4 show the results of SEM observation of the surface of the gold-cobalt alloy plating film before and after the heat treatment at 400 ° C. FIG. 3 is an SEM image before heat treatment (As-depo), and FIG. 4 is an SEM image after heat treatment. 3 and 4, a white spot-like region appears on the surface of the gold-cobalt alloy plating film after the heat treatment, and it can be seen that cobalt is oxidized by the heat treatment and the surface is altered. In Comparative Example 1, the hardness was maintained even after the heat treatment at 400 ° C., but the glossiness of the appearance was reduced by the heat treatment at 250 ° C., and the contact resistance was deteriorated by the heat treatment at 400 ° C. due to oxidation of cobalt.
［比較例２］
チオ尿素系化合物を含有しない、下記の組成のノンシアン系電解金めっき液を比較例２として調製した。金めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ８に調整した。
比較例２の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の量）
・トリエチレンテトラミン ２０ｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・グルタミン酸 ２０ｇ／Ｌ
[Comparative Example 2]
A non-cyanide electrolytic gold plating solution having the following composition and containing no thiourea-based compound was prepared as Comparative Example 2. The pH of the gold plating solution was adjusted to pH 8 by adding sodium hydroxide and sulfuric acid.
Gold plating solution composition of Comparative Example 2 • Gold sodium sulfite 10 g / L (amount of gold in gold plating solution)
・ Triethylenetetramine 20g / L
・ Sodium sulfite 40g / L
・ Glutamic acid 20g / L
ノンシアン金ストライクめっきを施したＮｉ板上に、比較例２の金めっき液を用い、液温６０℃、陰極電流密度０．３Ａ/ｄｍ２の条件で、実施例１と同じように厚さ１０μｍの金めっき皮膜を形成した。得られた金めっき皮膜のビッカース硬さ測定を行った結果、ＨＶ１０２であり硬質金めっき皮膜は得られなかった。 Using a gold plating solution of Comparative Example 2 on a Ni plate subjected to non-cyanide gold strike plating, at a solution temperature of 60 ° C. and a cathode current density of 0.3 A / dm 2, a thickness of 10 μm was obtained in the same manner as in Example 1. A gold plating film was formed. The Vickers hardness of the obtained gold plating film was measured. As a result, it was HV102, and no hard gold plating film was obtained.
［比較例３］
エチレンアミン化合物を含有しない、下記の組成のノンシアン系電解金めっき液を比較例３として調製した。金めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ８に調整した。
比較例３の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の量）
・チオ尿素 ６０ｍｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・アスパラギン酸 ２０ｇ／Ｌ
[Comparative Example 3]
A non-cyanide electrolytic gold plating solution having the following composition and containing no ethyleneamine compound was prepared as Comparative Example 3. The pH of the gold plating solution was adjusted to pH 8 by adding sodium hydroxide and sulfuric acid.
Gold plating solution composition of Comparative Example 3 • Gold sodium sulfite 10 g / L (amount of gold in gold plating solution)
・ Thiourea 60mg / L
・ Sodium sulfite 40g / L
・ Aspartic acid 20g / L
ノンシアン金ストライクめっきを施したＮｉ板上に、比較例３の金めっき液を用い、液温６０℃、陰極電流密度０．３Ａ/ｄｍ２の条件で、実施例１と同じように厚さ１０μｍの金めっき皮膜を形成した。得られた金めっき皮膜は光沢外観を有し、硬さ測定を行った結果、ＨＶ１７０であり、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。しかし、比較例３の金めっき液は、電解めっき中に濁りを生じ液が分解してしまい、安定した電解めっきを行うことはできなかった。 Using a gold plating solution of Comparative Example 3 on a Ni plate having been subjected to non-cyanide gold strike plating, a thickness of 10 μm as in Example 1 at a solution temperature of 60 ° C. and a cathode current density of 0.3 A / dm 2. A gold plating film was formed. The obtained gold plating film had a glossy appearance, and the hardness was measured. As a result, it was HV170 and the contact resistance (measuring load: 0.25 N) was 1 mΩ or less. However, the gold plating solution of Comparative Example 3 became turbid during electrolytic plating, and the solution was decomposed, so that stable electrolytic plating could not be performed.
［比較例４］
チオ尿素系化合物及びエチレンアミン化合物を含有しない、下記の組成のノンシアン系電解金めっき液を比較例４として調製した。金めっき液のｐＨは、水酸化ナトリウムと硫酸を添加してｐＨ８に調整した。
比較例4の金めっき液組成
・亜硫酸金ナトリウム １０ｇ／Ｌ（金めっき液中の金の量）
・亜ヒ酸ナトリウム ３ｍｇ／Ｌ
・亜硫酸ナトリウム ４０ｇ／Ｌ
・アルギニン ２０ｇ／Ｌ
[Comparative Example 4]
A non-cyanide electrolytic gold plating solution having the following composition and containing no thiourea-based compound and ethyleneamine compound was prepared as Comparative Example 4. The pH of the gold plating solution was adjusted to pH 8 by adding sodium hydroxide and sulfuric acid.
Gold plating solution composition of Comparative Example 4 • Gold sodium sulfite 10 g / L (amount of gold in gold plating solution)
・ Sodium arsenite 3mg / L
・ Sodium sulfite 40g / L
・ Arginine 20g / L
ノンシアン金ストライクめっきを施したＮｉ板上に、比較例４の金めっき液を用い、液温６０℃、陰極電流密度０．３Ａ/ｄｍ２の条件で、実施例１と同じように厚さ１０μｍの金めっき皮膜を形成した。得られた金めっき皮膜は光沢外観を有し、ビッカース硬さ測定を行った結果、ＨＶ１８１の硬質皮膜であった。また、接触抵抗(測定荷重：０．２５Ｎ)は１ｍΩ以下であった。しかし、この金めっき皮膜に大気下、２５０℃、３０分の熱処理を行ったところ、熱処理後の硬はＨＶ１１３に低下してしまい、硬度を維持することができなかった。 Using a gold plating solution of Comparative Example 4 on a Ni plate subjected to non-cyanide gold strike plating, at a solution temperature of 60 ° C. and a cathode current density of 0.3 A / dm 2, a thickness of 10 μm was obtained in the same manner as in Example 1. A gold plating film was formed. The obtained gold plating film had a glossy appearance, and was measured for Vickers hardness. As a result, it was a hard film of HV181. The contact resistance (measuring load: 0.25 N) was 1 mΩ or less. However, when the gold plating film was subjected to a heat treatment at 250 ° C. for 30 minutes in the atmosphere, the hardness after the heat treatment was reduced to HV113, and the hardness could not be maintained.
以上、本発明のノンシアン系電解金めっき液は、熱処理しても硬さの大きな低下がなく、変色や接触抵抗の劣化も生じない、耐熱性に優れた硬質金めっき皮膜を形成できる。また、毒性の高いシアン化合物を含有しないので、シアン系めっき液に比べて安全に作業ができ環境負荷も少ない。なお、本発明は上述した実施形態に限定されるものではなく、特許請求の範囲に記載された本発明の要旨の範囲内において、種々の変形、変更が可能である。 As described above, the non-cyanide-based electrolytic gold plating solution of the present invention can form a hard gold plating film having excellent heat resistance without causing a significant decrease in hardness even after heat treatment, and without causing discoloration or deterioration in contact resistance. Also, since it does not contain a highly toxic cyanide compound, it can be operated safely and has less environmental load than a cyan plating solution. The present invention is not limited to the embodiments described above, and various modifications and changes can be made within the scope of the present invention described in the appended claims.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111411376A (en) * | 2020-03-09 | 2020-07-14 | 中国工程物理研究院激光聚变研究中心 | Electroplating solution and electroplating method for cyanide-free sulfite system |
| CN112730731A (en) * | 2020-12-01 | 2021-04-30 | 成都四威高科技产业园有限公司 | Method for maintaining gold plating solution of sulfite |
| CN114108040A (en) * | 2020-08-25 | 2022-03-01 | 周大福珠宝文化产业园(武汉)有限公司 | Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process |
| CN114703520A (en) * | 2022-04-27 | 2022-07-05 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electroplating gold liquid, preparation method and application thereof, gold-plated part and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004360006A (en) * | 2003-06-04 | 2004-12-24 | Mitsubishi Chemicals Corp | Gold plating liquid, and gold plating method |
| WO2006049021A1 (en) * | 2004-11-02 | 2006-05-11 | Mitsubishi Chemical Corporation | Gold plating liquid and gold plating method |
| JP2006249485A (en) * | 2005-03-10 | 2006-09-21 | Japan Pure Chemical Co Ltd | Gold sulfite salt aqueous solution for gold plating |
| JP2010189753A (en) * | 2009-02-20 | 2010-09-02 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Plating bath and plating method using the same |
| JP2013023693A (en) * | 2011-07-14 | 2013-02-04 | Ishihara Chem Co Ltd | Imidazole ring-bonded type oxyalkylene compound and plating bath containing the compound |
-
2018
- 2018-06-11 JP JP2018111118A patent/JP6773079B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004360006A (en) * | 2003-06-04 | 2004-12-24 | Mitsubishi Chemicals Corp | Gold plating liquid, and gold plating method |
| WO2006049021A1 (en) * | 2004-11-02 | 2006-05-11 | Mitsubishi Chemical Corporation | Gold plating liquid and gold plating method |
| JP2006249485A (en) * | 2005-03-10 | 2006-09-21 | Japan Pure Chemical Co Ltd | Gold sulfite salt aqueous solution for gold plating |
| JP2010189753A (en) * | 2009-02-20 | 2010-09-02 | Daiwa Fine Chemicals Co Ltd (Laboratory) | Plating bath and plating method using the same |
| JP2013023693A (en) * | 2011-07-14 | 2013-02-04 | Ishihara Chem Co Ltd | Imidazole ring-bonded type oxyalkylene compound and plating bath containing the compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111411376A (en) * | 2020-03-09 | 2020-07-14 | 中国工程物理研究院激光聚变研究中心 | Electroplating solution and electroplating method for cyanide-free sulfite system |
| CN114108040A (en) * | 2020-08-25 | 2022-03-01 | 周大福珠宝文化产业园(武汉)有限公司 | Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process |
| CN112730731A (en) * | 2020-12-01 | 2021-04-30 | 成都四威高科技产业园有限公司 | Method for maintaining gold plating solution of sulfite |
| CN112730731B (en) * | 2020-12-01 | 2021-12-07 | 成都四威高科技产业园有限公司 | Method for maintaining gold plating solution of sulfite |
| CN114703520A (en) * | 2022-04-27 | 2022-07-05 | 深圳市联合蓝海黄金材料科技股份有限公司 | Cyanide-free electroplating gold liquid, preparation method and application thereof, gold-plated part and preparation method thereof |
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