JPH06316786A - Water-soluble iridium plating bath and plating method using the same - Google Patents
Water-soluble iridium plating bath and plating method using the sameInfo
- Publication number
- JPH06316786A JPH06316786A JP12467293A JP12467293A JPH06316786A JP H06316786 A JPH06316786 A JP H06316786A JP 12467293 A JP12467293 A JP 12467293A JP 12467293 A JP12467293 A JP 12467293A JP H06316786 A JPH06316786 A JP H06316786A
- Authority
- JP
- Japan
- Prior art keywords
- iridium
- plating
- plating bath
- water
- acid
- 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
- 238000007747 plating Methods 0.000 title claims abstract description 52
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 29
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims abstract description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 150000001408 amides Chemical class 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract 2
- -1 monocarboxylic acid salt Chemical class 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 150000002504 iridium compounds Chemical class 0.000 claims description 7
- 150000003140 primary amides Chemical class 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 3
- 238000003756 stirring Methods 0.000 abstract description 4
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 description 13
- 239000000203 mixture Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical compound NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 description 5
- IRJFCWPVAMSCQM-UHFFFAOYSA-H trisodium;iridium(3+);hexabromide Chemical compound [Na+].[Na+].[Na+].[Br-].[Br-].[Br-].[Br-].[Br-].[Br-].[Ir+3] IRJFCWPVAMSCQM-UHFFFAOYSA-H 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-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
- 230000008021 deposition Effects 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- POAPOGPNFCCSJW-UHFFFAOYSA-H Br[Ir](Br)(Br)(Br)(Br)Br.[Na] Chemical compound Br[Ir](Br)(Br)(Br)(Br)Br.[Na] POAPOGPNFCCSJW-UHFFFAOYSA-H 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 description 1
- 229930064664 L-arginine Natural products 0.000 description 1
- 235000014852 L-arginine Nutrition 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ZNJYTUSWSVUQTP-UHFFFAOYSA-J [Ir+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Ir+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZNJYTUSWSVUQTP-UHFFFAOYSA-J 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 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 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019262 disodium citrate Nutrition 0.000 description 1
- 239000002526 disodium citrate Substances 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical class [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 1
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 229940080818 propionamide Drugs 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は水溶性イリジウムめっ
き浴及びそのめっき方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble iridium plating bath and its plating method.
【０００２】[0002]
【従来の技術】イリジウムは、高い硬度を有するととも
に、高濃度の酸や王水、もしくはハロゲン類に対しても
優れた耐腐食性を示す金属であるが、その希少性と加工
の困難性のため工業用としてあまり使われておらず、そ
の応用範囲は所定の金属の硬化剤や触媒等に限られてい
た。しかし、近年のめっき技術の発展に伴い、イリジウ
ムめっきを装飾品のみならず防腐食材及び電気接点等の
材料として工業的に広く利用する技術が開発されてきて
いる。2. Description of the Related Art Iridium is a metal having high hardness and excellent corrosion resistance to high concentrations of acid, aqua regia, and halogens, but its rarity and the difficulty of processing it. Therefore, it has not been used for industrial use so much, and its application range was limited to hardeners and catalysts for specified metals. However, with the development of plating technology in recent years, a technology for industrially widely using iridium plating as a material for not only ornaments but also anticorrosion materials and electrical contacts has been developed.
【０００３】従来の水溶性イリジウムめっき浴の例とし
ては、イリジウム化合物としてヘキサクロロイリジウム
（III ）酸塩、ヘキサクロロイリジウム（IV）酸塩、塩
化イリジウム（III ）酸塩、硫酸イリジウム（III ）酸
塩、硫酸イリジウム（IV）酸塩、その他イリジウムの硝
酸塩や亜硝酸塩を用いたものが知られている。Examples of conventional water-soluble iridium plating baths include hexachloroiridium (III) salts, hexachloroiridium (IV) salts, iridium chloride (III) salts, and iridium sulfate (III) salts as iridium compounds. It is known to use iridium (IV) sulfate and other iridium nitrates and nitrites.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな従来の水溶性イリジウムめっき浴にあっては、陽極
側で酸化物が発生したり、めっき液が不安定で分解した
りしやすいという問題があった。加えて、電流効率も最
大で６５パーセント程度しかなく、更にまた非常に低い
電流密度でしか最大析出効率が得られないため、めっき
速度が非常に小さいという問題もあった。また、この従
来の水溶性イリジウムめっき浴は、めっき速度が一定で
ないという問題もあり、これは実用的な膜厚が安定して
得られないということにつながるものである。このよう
に、従来の水溶性イリジウムめっき浴はあまり実用的で
はなく、この点が、工業用としてイリジウムめっきがあ
まり広く利用されていない一因となっていた。However, in such a conventional water-soluble iridium plating bath, there are problems that oxides are generated on the anode side and the plating solution is unstable and easily decomposed. there were. In addition, the current efficiency is only about 65% at maximum, and the maximum deposition efficiency can be obtained only at a very low current density, so that there is a problem that the plating rate is very low. Further, this conventional water-soluble iridium plating bath also has a problem that the plating rate is not constant, which leads to the fact that a practical film thickness cannot be obtained stably. As described above, the conventional water-soluble iridium plating bath is not very practical, which is one reason why iridium plating is not widely used for industrial purposes.
【０００５】本発明は、このような従来の技術に着目し
てなされたものであり、安定で分解しにくく、高い電流
効率と速いめっき速度を有する実用的な水溶性イリジウ
ムめっき浴を提供するものである。The present invention has been made by paying attention to such a conventional technique, and provides a practical water-soluble iridium plating bath which is stable and difficult to decompose, has a high current efficiency and a high plating rate. Is.
【０００６】[0006]
【課題を解決するための手段】この発明に係る水溶性イ
リジウムめっき浴は、イリジウム化合物として、アニオ
ン成分がハロゲンであるイリジウム（III ）錯塩に、飽
和モノカルボン酸、飽和モノカルボン酸塩、飽和ジカル
ボン酸、飽和ジカルボン酸塩、飽和ヒドロキシカルボン
酸、飽和ヒドロキシカルボン酸塩、第１アミド、尿素か
らなる群より選ばれた一種以上の化合物を加え攪拌した
ものを使用するものとしている。The water-soluble iridium plating bath according to the present invention comprises, as an iridium compound, an iridium (III) complex salt whose anion component is halogen, a saturated monocarboxylic acid, a saturated monocarboxylic acid salt and a saturated dicarboxylic acid salt. It is assumed that one or more compounds selected from the group consisting of an acid, a saturated dicarboxylic acid salt, a saturated hydroxycarboxylic acid, a saturated hydroxycarboxylic acid salt, a primary amide, and urea are added and stirred.
【０００７】そして、イリジウムは金属イリジウム濃度
で１〜２００ｇ／ｌ含有するものとし、好ましくは１０
〜２０ｇ／ｌ存在させることができる。イリジウム濃度
が１ｇ／ｌより少ないと電流密度の上限が小さくなって
実用に供することが難しくなり、２００ｇ／ｌより多い
と飽和してイリジウムが溶解できなくなるとともにコス
トが高価になり実用上不適となる。イリジウム（III ）
錯塩としては、ヘキサクロロイリジウム（III ）酸塩、
ヘキサブロモイリジウム（III ）酸塩、ヘキサフルオロ
イリジウム（III ）酸塩〔好ましくはヘキサブロモイリ
ジウム（III ）酸ナトリウム、ヘキサクロロイリジウム
（III ）酸ナトリウム〕等を採用できる。Iridium is contained in a metal iridium concentration of 1 to 200 g / l, preferably 10
~ 20 g / l can be present. If the iridium concentration is less than 1 g / l, the upper limit of the current density becomes small, making it difficult to put into practical use. If the iridium concentration is more than 200 g / l, it becomes saturated and iridium cannot be dissolved, and the cost becomes high, making it unsuitable for practical use. . Iridium (III)
As the complex salt, hexachloroiridium (III) salt,
Hexabromoiridium (III) acid salt, hexafluoroiridium (III) acid salt [preferably sodium hexabromoiridium (III) acid, sodium hexachloroiridium (III) acid] and the like can be employed.
【０００８】更に、飽和モノカルボン酸、飽和モノカル
ボン酸塩、飽和ジカルボン酸、飽和ジカルボン酸塩、飽
和ヒドロキシカルボン酸、飽和ヒドロキシカルボン酸
塩、第１アミド、尿素からなる群より選ばれた一種以上
の化合物は、０．００１〜１．０ｍｏｌ／ｌ添加するも
のとし、好ましくは０．０１〜０．２ｍｏｌ／ｌ添加す
るようにしている。そして、この化合物としては例えば
マロン酸二ナトリウム、酢酸、シュウ酸等を採用でき
（好ましくはマロン酸二ナトリウム）、その添加量を
０．００１〜１．０ｍｏｌ／ｌとしたのは、０．００１
ｍｏｌ／ｌより少ないと添加による効果がほとんど現れ
ないためであり、１．０ｍｏｌ／ｌより多いと析出が妨
げられるためである。Further, one or more selected from the group consisting of saturated monocarboxylic acid, saturated monocarboxylic acid salt, saturated dicarboxylic acid, saturated dicarboxylic acid salt, saturated hydroxycarboxylic acid, saturated hydroxycarboxylic acid salt, primary amide, and urea. The compound (1) is added in an amount of 0.001 to 1.0 mol / l, preferably 0.01 to 0.2 mol / l. And, as this compound, for example, disodium malonate, acetic acid, oxalic acid, etc. can be adopted (preferably disodium malonate), and the addition amount thereof is 0.001-1.0 mol / l is 0.001
This is because if it is less than mol / l, the effect of the addition hardly appears, and if it is more than 1.0 mol / l, precipitation is prevented.
【０００９】更にまた、本発明に係る水溶性イリジウム
めっき方法は、操作条件をｐＨ１〜８、温度５０〜９８
℃、電流密度０．０１〜３．０Ａ／ｄｍ2 とし、好まし
くはＰＨ４〜５、温度８０〜９０℃、電流密度０．１〜
０．２Ａ／ｄｍ2 の操作条件で用いる。ＰＨ１〜８とし
たのは、ＰＨが１より小さいと電流密度の上限が小さく
なって実用的でなくなるためであり、ＰＨが８より大き
いと水酸化物を生成し沈殿が生ずるからである。そして
温度が５０℃より低いと極端に析出が起こりにくくな
り、温度が９８℃より高いと水の蒸発が激しくなり実用
上好ましくなくなる。そしてまた、電流密度が０・０１
Ａ／ｄｍ2 より低い場合は析出速度が極端に小さくな
り、３・０Ａ／ｄｍ2 より高い電流密度の場合は水素の
発生が起こり、析出物が析出しなくなる。Furthermore, in the water-soluble iridium plating method according to the present invention, the operating conditions are pH 1-8 and temperature 50-98.
C, current density 0.01 to 3.0 A / dm 2 , preferably PH 4 to 5, temperature 80 to 90 ° C., current density 0.1.
Used under operating conditions of 0.2 A / dm 2 . The reason why the pH is set to 1 to 8 is that if the PH is less than 1, the upper limit of the current density becomes small and it becomes unpractical, and if the PH is more than 8, hydroxide is generated and precipitation occurs. When the temperature is lower than 50 ° C., precipitation hardly occurs, and when the temperature is higher than 98 ° C., water is vigorously evaporated, which is not preferable for practical use. And again, the current density is 0.01
When it is lower than A / dm 2, the deposition rate becomes extremely small, and when the current density is higher than 3.0 A / dm 2 , hydrogen is generated and the deposit does not deposit.
【００１０】[0010]
【実施例】次に実施例によってこの発明を更に詳細に説
明する。実施例１ ヘキサブロモイリジウム（III ）酸ナトリウム（メタル濃度で）１０ｇ／ｌ ホウ酸 ４０ｇ／ｌ マロン酸二ナトリウム ０．０２ｍｏｌ／ｌ ｐＨ ５．０ 温度 ８５℃ 電流密度 ０．１５Ａ／ｄｍ2 本実施例では、イリジウム化合物として、上記ヘキサブ
ロモイリジウム（III）酸ナトリウムに、「ジカルボン
酸塩」としてのマロン酸二ナトリウムを加え、ホットバ
スで８５℃に保ちながらマグネチックスターラで１時間
攪拌したものを用いた。そして、予め真鍮片に金ストラ
イクめっきを施し、更にその上に１μｍの金めっきを施
した試験片に、上記の条件でめっきを行なったところ、
膜厚が８μｍの光沢ある析出物が得られた。そしてこの
析出物は硬度、密着性、耐熱性、ボンディング性等にお
いて実用上十分な特性を備えていることが確認できた。
また、電流効率は１００％であり、めっき速度は１．５
μｍ／ｈであった。The present invention will be described in more detail with reference to the following examples. Example 1 Sodium hexabromoiridium (III) (at metal concentration) 10 g / l Boric acid 40 g / l Disodium malonate 0.02 mol / l pH 5.0 Temperature 85 ° C. Current density 0.15 A / dm 2 Conducted In the example, as an iridium compound, disodium malonate as a “dicarboxylate” was added to the above sodium hexabromoiridium (III), and the mixture was stirred with a magnetic stirrer for 1 hour while maintaining the temperature at 85 ° C. in a hot bath. Using. Then, a brass piece was subjected to gold strike plating in advance, and a test piece having 1 μm of gold plated thereon was plated under the above conditions,
A glossy precipitate with a film thickness of 8 μm was obtained. It was confirmed that this precipitate has practically sufficient characteristics in terms of hardness, adhesion, heat resistance, bondability, and the like.
The current efficiency is 100% and the plating rate is 1.5.
It was μm / h.
【００１１】なお、上記と同様の組成及び条件におい
て、マロン酸二ナトリウムを以下の化合物に代えてそれ
ぞれめっきを行なったところ、次のような結果が得られ
た。即ち「モノカルボン酸」としての酢酸０．２ｍｏｌ
／ｌを用いた場合は電流効率８１％、膜厚１．９ μ
ｍ、めっき速度１．２μｍ／ｈとなり、「ジカルボン
酸」としてのシュウ酸０．０２ｍｏｌ／ｌを用いた場合
は電流効率９３％、膜厚２．６μｍ、めっき速度１．４
μｍ／ｈとなった。そしてまた「ヒドロキシカルボン
酸」としての酒石酸０．２ｍｏｌ／ｌを用いた場合は電
流効率７４％、膜厚１．１μｍ、めっき速度１．１μｍ
／ｈとなり、「ヒドロキシカルボン酸塩」としてのクエ
ン酸二ナトリウム０．２ｍｏｌ／ｌを用いた場合は電流
効率８７％、膜厚２．８μｍ、めっき速度１．３μｍ／
ｈとなった。外観等の他の特性に関してはそれぞれ上記
マロン酸ニナトリウムを用いた場合と同様の効果が得ら
れた。The following results were obtained when plating was performed under the same composition and conditions as described above, substituting the following compounds for disodium malonate. That is, 0.2 mol of acetic acid as "monocarboxylic acid"
/ L used current efficiency 81%, film thickness 1.9μ
m, plating rate 1.2 μm / h, when using oxalic acid 0.02 mol / l as “dicarboxylic acid”, current efficiency 93%, film thickness 2.6 μm, plating rate 1.4
μm / h. And when tartaric acid 0.2 mol / l as "hydroxycarboxylic acid" is used, current efficiency is 74%, film thickness is 1.1 μm, plating rate is 1.1 μm.
/ H, and when using 0.2 mol / l of disodium citrate as the “hydroxycarboxylic acid salt”, current efficiency was 87%, film thickness was 2.8 μm, plating rate was 1.3 μm /
It became h. With respect to other characteristics such as appearance, the same effects as in the case of using the above disodium malonate were obtained.
【００１２】実施例２ ヘキサクロロイリジウム（III ）酸ナトリウム（メタル濃度で）１０ｇ／ｌ ホウ酸 ４０ｇ／ｌ マロン酸二ナトリウム ０．０２ｍｏｌ／ｌ ｐＨ ５ 温度 ８５℃ 電流密度 ０．１５Ａ／ｄｍ2 本実施例では、イリジウム化合物として、上記ヘキサク
ロロイリジウム（III）酸ナトリウムに、マロン酸二ナ
トリウムを加え、ホットバスで８５℃に保ちながらマグ
ネチックスターラで３０分攪拌したものを用いた。そし
て、予め真鍮片に金ストライクめっきを施し、更にその
上に１μｍの金めっきを施した試験片に、上記の条件で
めっきを行なったところ、膜厚が３μｍの光沢ある析出
物が得られた。そしてこの析出物は硬度、密着性、耐熱
性、ボンディング性等において実用上十分な特性を備え
ていることが確認できた。また、電流効率は９８％であ
り、めっき速度は１．５μｍ／ｈであった。 Example 2 Sodium hexachloroiridium (III) (at metal concentration) 10 g / l Boric acid 40 g / l Disodium malonate 0.02 mol / l pH 5 Temperature 85 ° C. Current density 0.15 A / dm 2 Implementation In the example, as the iridium compound, there was used one obtained by adding disodium malonate to the above sodium hexachloroiridium (III) and stirring the mixture with a magnetic stirrer for 30 minutes while maintaining the temperature at 85 ° C. in a hot bath. Then, a brass piece was gold-strike plated in advance, and a test piece having 1 μm of gold plated thereon was plated under the above conditions, and a glossy precipitate having a film thickness of 3 μm was obtained. . It was confirmed that this precipitate has practically sufficient characteristics in terms of hardness, adhesion, heat resistance, bondability, and the like. The current efficiency was 98%, and the plating rate was 1.5 μm / h.
【００１３】なお、上記と同様の組成及び条件におい
て、マロン酸二ナトリウムに代えて「モノカルボン酸
塩」としてのプロピオン酸ナトリウム０．２ｍｏｌ／ｌ
を用いたところ、電流効率６０％、膜厚０．１μｍ、め
っき速度０．９μｍ／ｈとなり、外観等の他の特性に関
しては上記マロン酸ニナトリウムを用いた場合と同様の
効果が得られた。Under the same composition and conditions as described above, sodium propionate 0.2 mol / l as "monocarboxylate" was used instead of disodium malonate.
The current efficiency was 60%, the film thickness was 0.1 μm, and the plating rate was 0.9 μm / h. With respect to other characteristics such as appearance, the same effects as those obtained by using the disodium malonate were obtained. .
【００１４】実施例３ ヘキサブロモイリジウム（III ）酸ナトリウム（メタル濃度で）１０ｇ／ｌ ホウ酸 ４０ｇ／ｌ マロン酸二ナトリウム ０．０２ｍｏｌ／ｌ ｐＨ ５ 温度 ８５℃ 電流密度 ０．５Ａ／ｄｍ2 本実施例では、イリジウム化合物として、上記ヘキサブ
ロモイリジウム（III）酸ナトリウムに、マロン酸二ナ
トリウムを加え、ホットバスで８５℃に保ちながらマグ
ネチックスターラで１時間攪拌したものを用いた。そし
て、予め真鍮片に金ストライクめっきを施し、更にその
上に１μｍの金めっきを施した試験片に、上記の条件で
めっきを行なったところ、膜厚が５μｍの光沢ある析出
物が得られた。そしてこの析出物は硬度、密着性、耐熱
性、ボンディング性等において実用上十分な特性を備え
ていることが確認できた。また、電流効率は９０％であ
り、めっき速度は５μｍ／ｈであった。 Example 3 Sodium hexabromoiridium (III) (at metal concentration) 10 g / l Boric acid 40 g / l Disodium malonate 0.02 mol / l pH 5 Temperature 85 ° C. Current density 0.5 A / dm 2 pieces In the examples, as the iridium compound, the one obtained by adding disodium malonate to the above-mentioned sodium hexabromoiridium (III) and stirring the mixture for 1 hour with a magnetic stirrer while keeping it at 85 ° C. in a hot bath was used. A brass piece was gold-strike plated in advance, and a test piece having 1 μm of gold plated thereon was plated under the above conditions. As a result, a glossy precipitate having a film thickness of 5 μm was obtained. . It was confirmed that this precipitate has practically sufficient characteristics in terms of hardness, adhesion, heat resistance, bondability, and the like. The current efficiency was 90%, and the plating rate was 5 μm / h.
【００１５】実施例４ ヘキサブロモイリジウム（III ）酸ナトリウム（メタル濃度で）１０ｇ／ｌ ホウ酸 ４０ｇ／ｌ マロンアミド ０．２ｍｏｌ／ｌ ｐＨ ５ 温度 ８５℃ 電流密度 ０．１５Ａ／ｄｍ2 本実施例では、イリジウム化合物として、上記ヘキサブ
ロモイリジウム（III）酸ナトリウムに、マロンアミド
を加え、ホットバスで８５℃に保ちながらマグネチック
スターラで１時間攪拌したものを用いた。そして、予め
真鍮片に金ストライクめっきを施し、更にその上に１μ
ｍの金めっきを施した試験片に、上記の条件でめっきを
行なったところ、膜厚が３μｍの光沢ある析出物が得ら
れた。そしてこの析出物は硬度、密着性、耐熱性、ボン
ディング性等、実用上十分な特性を備えていることが確
認できた。また、電流効率は８４％であり、めっき速度
は１．２μｍ／ｈであった。 Example 4 Sodium hexabromoiridium (III) (at metal concentration) 10 g / l Boric acid 40 g / l Malonamide 0.2 mol / l pH 5 Temperature 85 ° C. Current density 0.15 A / dm 2 In this example As the iridium compound, the one obtained by adding malonamide to the above sodium hexabromoiridium (III) and stirring the mixture with a magnetic stirrer for 1 hour while maintaining the temperature at 85 ° C. in a hot bath was used. Then, gold strike plating is applied to the brass piece in advance, and 1 μm is further applied on it.
When a m-plated test piece was plated under the above conditions, a glossy precipitate having a film thickness of 3 μm was obtained. It was confirmed that this precipitate had practically sufficient characteristics such as hardness, adhesion, heat resistance, and bondability. The current efficiency was 84%, and the plating rate was 1.2 μm / h.
【００１６】なお、上記と同様の組成及び条件におい
て、マロンアミドに代えてプロピオンアミド０．２ｍｏ
ｌ／ｌを用いてめっきを行なったところ、電流効率７７
％、膜厚０．１μｍ、めっき速度１．２μｍ／ｈとな
り、同じくマロンアミドに代えて尿素０．２ｍｏｌ／ｌ
を用いたところ、電流効率８５％、膜厚２．８μｍ、め
っき速度１．３μｍ／ｈとなった。外観等の他の特性に
関しては上記マロンアミドを用いた場合と同様の効果が
得られた。Under the same composition and conditions as described above, propionamide 0.2 mo was used instead of malonamide.
When plating was performed using 1 / l, the current efficiency was 77
%, Film thickness 0.1 μm, plating rate 1.2 μm / h, and urea 0.2 mol / l instead of malonamide.
Was used, the current efficiency was 85%, the film thickness was 2.8 μm, and the plating rate was 1.3 μm / h. With respect to other characteristics such as appearance, the same effects as those obtained when the above malonamide was used were obtained.
【００１７】比較例 実施例１と同様の組成及び条件において、マロン酸二ナ
トリウムを下記化合物に代えてそれぞれめっきを行なっ
たところ、次のような結果が得られた。即ち不飽和カル
ボン酸としてアクリル酸０．２ｍｏｌ／ｌを用いた場合
は電流効率０％、同じくマレイン酸を用いた場合も電流
効率０％となった。更に、第２アミド（酸イミド）とし
てスクシンイミド０．２ｍｏｌ／ｌを用いた場合は電流
効率０％であった。更にまた、アミノ酸としてグリシン
０．２ｍｏｌ／ｌを用いた場合は電流効率５９％、Ｌ−
アスパラギン酸０．２ｍｏｌ／ｌを用いた場合は電流効
率０％、Ｌ−アルギニン０．２ｍｏｌ／ｌを用いた場合
は電流効率０％であった。 Comparative Example Under the same composition and conditions as in Example 1, plating was carried out by replacing disodium malonate with the following compound, and the following results were obtained. That is, the current efficiency was 0% when 0.2 mol / l of acrylic acid was used as the unsaturated carboxylic acid, and the current efficiency was 0% when maleic acid was also used. Furthermore, when succinimide 0.2 mol / l was used as the second amide (acid imide), the current efficiency was 0%. Furthermore, when glycine 0.2 mol / l was used as the amino acid, the current efficiency was 59%, L-
The current efficiency was 0% when aspartic acid 0.2 mol / l was used, and the current efficiency was 0% when L-arginine 0.2 mol / l was used.
【００１８】[0018]
【発明の効果】以上説明したように、本発明にかかる水
溶性イリジウムめっき浴及びそのめっき方法は、飽和モ
ノカルボン酸、飽和モノカルボン酸塩、飽和ジカルボン
酸、飽和ジカルボン酸塩、飽和ヒドロキシカルボン酸、
飽和ヒドロキシカルボン酸塩、第１アミド、尿素からな
る群より選ばれた一種以上の化合物を加えて反応させた
イリジウム（III ）錯塩を用いることによって、めっき
浴が分解しにくくなり、浴の安定性が増すという効果が
ある。そしてまた、本発明にかかるめっき浴及びそのめ
っき方法は、電流効率の減少の割合を非常に小さく抑え
ることができるため実用的なめっき速度が得られるとと
もに、最大１００％の電流効率が得られるという効果が
ある。As described above, the water-soluble iridium plating bath according to the present invention and the plating method therefor are a saturated monocarboxylic acid, a saturated monocarboxylic acid salt, a saturated dicarboxylic acid, a saturated dicarboxylic acid salt, and a saturated hydroxycarboxylic acid. ,
By using an iridium (III) complex salt obtained by reacting with one or more compounds selected from the group consisting of saturated hydroxycarboxylic acid salt, primary amide and urea, the plating bath is less likely to decompose and the stability of the bath is improved. The effect is to increase. Further, the plating bath and the plating method thereof according to the present invention can suppress the reduction rate of the current efficiency to a very small level, so that a practical plating speed can be obtained and a current efficiency of up to 100% can be obtained. effective.
Claims (4)
ム（III ）錯塩に、飽和モノカルボン酸、飽和モノカル
ボン酸塩、飽和ジカルボン酸、飽和ジカルボン酸塩、飽
和ヒドロキシカルボン酸、飽和ヒドロキシカルボン酸
塩、第１アミド、尿素からなる群より選ばれた一種以上
の化合物を加えて撹拌したものを、イリジウム化合物と
して用いる水溶性イリジウムめっき浴。1. An iridium (III) complex salt whose anion component is halogen is added to a saturated monocarboxylic acid, saturated monocarboxylic acid salt, saturated dicarboxylic acid, saturated dicarboxylic acid salt, saturated hydroxycarboxylic acid, saturated hydroxycarboxylic acid salt, A water-soluble iridium plating bath in which one or more compounds selected from the group consisting of 1 amide and urea are added and stirred and used as an iridium compound.
である、請求項１記載の水溶性イリジウムめっき浴。2. A metal iridium concentration of 1 to 200 g / l
The water-soluble iridium plating bath according to claim 1, which is
カルボン酸、ジカルボン酸塩、ヒドロキシカルボン酸、
ヒドロキシカルボン酸塩、第１アミド、尿素からなる群
より選ばれた一種以上の化合物の濃度が０．００１〜
１．０ｍｏｌ／ｌである、請求項１又は２記載の水溶性
イリジウムめっき浴。3. A monocarboxylic acid, a monocarboxylic acid salt, a dicarboxylic acid, a dicarboxylic acid salt, a hydroxycarboxylic acid,
The concentration of one or more compounds selected from the group consisting of hydroxycarboxylic acid salts, primary amides, and urea is 0.001-
The water-soluble iridium plating bath according to claim 1 or 2, which has a concentration of 1.0 mol / l.
浴を使用し、ｐＨ１〜８、温度５０〜９８℃、電流密度
０．０１〜３．０Ａ／ｄｍ2 の操作条件でめっきする水
溶性イリジウムめっき方法。4. Using the plating bath according to any one of claims 1 to 3, plating is performed under operating conditions of pH 1 to 8, temperature of 50 to 98 ° C. and current density of 0.01 to 3.0 A / dm 2. Water-soluble iridium plating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12467293A JP3256912B2 (en) | 1993-04-30 | 1993-04-30 | Water-soluble iridium plating bath and plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12467293A JP3256912B2 (en) | 1993-04-30 | 1993-04-30 | Water-soluble iridium plating bath and plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06316786A true JPH06316786A (en) | 1994-11-15 |
| JP3256912B2 JP3256912B2 (en) | 2002-02-18 |
Family
ID=14891210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12467293A Expired - Lifetime JP3256912B2 (en) | 1993-04-30 | 1993-04-30 | Water-soluble iridium plating bath and plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3256912B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039778A (en) * | 2005-08-05 | 2007-02-15 | Nisshin Kasei Kk | Iridium plating solution and iridium plating method |
| JP2008088520A (en) * | 2006-10-03 | 2008-04-17 | Nisshin Kasei Kk | Plating method |
| JP2008088519A (en) * | 2006-10-03 | 2008-04-17 | Nisshin Kasei Kk | Solution for plating iridium-cobalt alloy |
| JP2010248552A (en) * | 2009-04-14 | 2010-11-04 | Electroplating Eng Of Japan Co | Iridium plating solution and plating method thereof |
| CN102400190A (en) * | 2010-09-17 | 2012-04-04 | 日本电镀工程股份有限公司 | Iridium plating solution and electroplate method thereof |
| CN104195604A (en) * | 2014-09-17 | 2014-12-10 | 朱忠良 | Iridium plating solution for inhibiting crack generation and plating method thereof, and coated substance |
| CN105506685A (en) * | 2016-01-25 | 2016-04-20 | 东莞联桥电子有限公司 | Novel rhodanizing process for PCBs |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892498B (en) * | 2010-06-24 | 2011-12-07 | 北京航空航天大学 | Method for preparing iridium layer in ionic liquid electro-deposition solution through electro-deposition |
| TWI495767B (en) * | 2010-09-02 | 2015-08-11 | Electroplating Eng | Iridium plating solution and method of plating using the same |
-
1993
- 1993-04-30 JP JP12467293A patent/JP3256912B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007039778A (en) * | 2005-08-05 | 2007-02-15 | Nisshin Kasei Kk | Iridium plating solution and iridium plating method |
| JP4751126B2 (en) * | 2005-08-05 | 2011-08-17 | 日進化成株式会社 | Iridium plating solution and iridium plating method |
| JP2008088520A (en) * | 2006-10-03 | 2008-04-17 | Nisshin Kasei Kk | Plating method |
| JP2008088519A (en) * | 2006-10-03 | 2008-04-17 | Nisshin Kasei Kk | Solution for plating iridium-cobalt alloy |
| JP2010248552A (en) * | 2009-04-14 | 2010-11-04 | Electroplating Eng Of Japan Co | Iridium plating solution and plating method thereof |
| CN102400190A (en) * | 2010-09-17 | 2012-04-04 | 日本电镀工程股份有限公司 | Iridium plating solution and electroplate method thereof |
| CN104195604A (en) * | 2014-09-17 | 2014-12-10 | 朱忠良 | Iridium plating solution for inhibiting crack generation and plating method thereof, and coated substance |
| CN105506685A (en) * | 2016-01-25 | 2016-04-20 | 东莞联桥电子有限公司 | Novel rhodanizing process for PCBs |
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| Publication number | Publication date |
|---|---|
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