JPH03287781A - Production of pd-ag alloy plating film by electroless plating and electroless plating bath used therefor - Google Patents
Production of pd-ag alloy plating film by electroless plating and electroless plating bath used thereforInfo
- Publication number
- JPH03287781A JPH03287781A JP8745890A JP8745890A JPH03287781A JP H03287781 A JPH03287781 A JP H03287781A JP 8745890 A JP8745890 A JP 8745890A JP 8745890 A JP8745890 A JP 8745890A JP H03287781 A JPH03287781 A JP H03287781A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- plating
- silver
- palladium
- plating film
- 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.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 81
- 238000007772 electroless plating Methods 0.000 title claims abstract description 24
- 229910001316 Ag alloy Inorganic materials 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052709 silver Inorganic materials 0.000 claims description 27
- 239000004332 silver Substances 0.000 claims description 23
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 150000002940 palladium Chemical class 0.000 claims description 19
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- -1 amine compound Chemical class 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 52
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 229910045601 alloy Inorganic materials 0.000 description 11
- 239000000956 alloy Substances 0.000 description 11
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000009713 electroplating Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 3
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000012493 hydrazine sulfate Substances 0.000 description 3
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910021124 PdAg Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、無電解メッキ法によるＰｄ−Ａｇ合金メッキ
膜の製造法及びそれに使用する無電解メッキ浴に関し、
特に複雑な形状の物品にも均一な厚みのＰｄ−Ａｇメッ
キ膜を形成させることができる前記メッキ膜の製造法及
び無電解メッキ浴に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a Pd-Ag alloy plating film by an electroless plating method and an electroless plating bath used therein.
In particular, the present invention relates to a method of manufacturing the plating film and an electroless plating bath that can form a Pd-Ag plating film of uniform thickness even on articles with complicated shapes.
パラジウム膜は電子部品を形成するために用いられ、特
にパラジウム合金膜は接点やコネクターなどの電子部品
を形成するのに用いられ、それは電子部品に多用されて
いる金の代替品となるといわれている。そのためパラジ
ウム合金膜が膜形成手段によって形成されるが、これら
の用途のための膜形成手段としてはほとんどすべて電気
メッキ法が用いられており、無電解メッキではメッキ膜
の形成が困難であるとされてきた。最近、Ｐｄ−Ｎ１−
Ｐ合金膜が無電解メッキにより形成されるとした報告が
でてきたが、Ｐｄ−Ａｇ合金膜についてはまだない。Palladium films are used to form electronic parts, and palladium alloy films in particular are used to form electronic parts such as contacts and connectors, and it is said to be a substitute for gold, which is often used in electronic parts. . For this reason, palladium alloy films are formed by film forming means, but electroplating is almost always used as a film forming means for these applications, and it is said that it is difficult to form plated films with electroless plating. It's here. Recently, Pd-N1-
Although there have been reports that a P alloy film is formed by electroless plating, there is no report yet on a Pd-Ag alloy film.
〔発明が解決しようとする課題］
上記したように、一般に合金膜を製造するのに電気メッ
キ法による場合は、基体が導電体でなければ行うことが
できないから、特定のものにしか適用することができず
、しかも、電気メッキにより銀を析出させるさいにはそ
の樹板状結晶が成長し易いこともあって、銀合金のメッ
キは状態の良い薄膜を得ることが難しい。ただ、電気メ
ッキ法の場合、電圧を与えて金属イオンを強制的に電極
に導びき金属として析出させるため、２種以上の金属イ
オンがあるとき電極電位の低い方の金属イオンの電極電
位よりもさらに低い電位を与えることにより、全部の種
類の金属イオンを同時に析出させることができるので、
所定組成の合金メッキ膜を形成することが容易である。[Problems to be Solved by the Invention] As mentioned above, when electroplating is generally used to produce an alloy film, it cannot be performed unless the substrate is a conductor, so it can only be applied to specific products. Furthermore, when silver is deposited by electroplating, the dendritic crystals tend to grow, making it difficult to obtain a thin film in good condition when plating silver alloys. However, in the case of electroplating, since a voltage is applied to forcibly guide metal ions to the electrode and deposit them as metal, when there are two or more types of metal ions, the electrode potential is higher than that of the metal ion with a lower electrode potential. By applying an even lower potential, all types of metal ions can be precipitated at the same time.
It is easy to form an alloy plating film with a predetermined composition.
しかし、無電解メッキによるときにはどのような基体に
も均一な薄膜を形成することができる利点があるが、無
電解メッキの場合金属イオンが還元されて金属となって
析出するという機構によっているので、合金メッキをす
るため液中に２種以上の金属イオンを混在させると、還
元され易い、すなわち酸化還元電位の高い金属イオンか
ら還元されてその金属が先に析出するという傾向があり
、このため目的とする合金メッキ膜が得られないという
問題があった。特に、Ｐｄ−Ａｇ合金メッキ膜を無電解
メッキ法で得ようとする場合には、条件によっては銀だ
けが析出しまうという場合もあり、目的とする組成のＰ
ｄ−Ａｇ合金メッキ膜を得ることができなかった。However, although electroless plating has the advantage of being able to form a uniform thin film on any substrate, electroless plating relies on a mechanism in which metal ions are reduced and precipitated as metal. When two or more types of metal ions are mixed in a solution for alloy plating, they tend to be reduced more easily, that is, metal ions with higher redox potentials tend to be reduced and precipitate first. There was a problem in that it was not possible to obtain an alloy plating film. In particular, when attempting to obtain a Pd-Ag alloy plating film by electroless plating, only silver may be deposited depending on the conditions, and Pd-Ag alloy plating film with the desired composition may
A d-Ag alloy plating film could not be obtained.
本発明は、均一な厚さのＰｄ−Ａｇ合金膜を無電解メッ
キ法により製造する方法及びそれに使用する無電解メッ
キ浴を得ることを目的とするものである。The object of the present invention is to provide a method for manufacturing a Pd-Ag alloy film of uniform thickness by electroless plating, and an electroless plating bath for use therein.
Ｃ課題を解決するための手段］ 本発明は、次の手段により上記の目的を達成した。Means to solve problem C] The present invention has achieved the above object by the following means.
（１）パラジウム塩、銀塩、アンモニア又はアミン化合
物の少なくとも一つからなる塩基、ヒドラジン又はヒド
ラジニウム塩の少なくとも一つからなる還元剤、アミノ
多価酢酸又はその塩の少なくとも一つからなるキレート
剤を含有し、かつパラジウム塩に対する銀塩の比率は生
成すべきＰｄＡｇ合金メッキ膜のパラジウム対銀の比率
よりも小さく維持したメッキ浴を用いて、触媒活性なる
担体上にＰｄ−Ａｇ合金メッキ膜を析出させることを特
徴とするＰｄ−Ａｇ合金メッキ膜の製造法。(1) A base consisting of at least one of palladium salt, silver salt, ammonia or an amine compound, a reducing agent consisting of at least one of hydrazine or hydrazinium salt, and a chelating agent consisting of at least one of amino polyvalent acetic acid or its salt. Depositing a Pd-Ag alloy plating film on a catalytically active support using a plating bath containing silver salt to palladium salt and keeping the ratio of silver salt to palladium salt smaller than the ratio of palladium to silver in the PdAg alloy plating film to be produced. A method for producing a Pd-Ag alloy plating film, the method comprising:
（２）パラジウム塩、銀塩、アンモニア又はアミン化合
物の少なくとも一つからなる塩基、ヒドラジン又はヒド
ラジニウム塩の少なくとも一つからなる還元剤、アミノ
多価酢酸又はその塩の少なくとも一つからなるキレート
剤を含有し、かつパラジウム塩に対する銀塩の比率は生
成すべきＰｄＡｇ合金メッキ膜のパラジウム対銀の比率
よりも小さく維持したことを特徴とするＰｄ−Ａｇ合金
メッキ用無電解メッキ浴。(2) A base consisting of at least one of palladium salt, silver salt, ammonia or an amine compound, a reducing agent consisting of at least one of hydrazine or hydrazinium salt, and a chelating agent consisting of at least one of amino polyvalent acetic acid or its salt. 1. An electroless plating bath for Pd-Ag alloy plating, characterized in that the ratio of silver salt to palladium salt is maintained smaller than the ratio of palladium to silver in a PdAg alloy plating film to be produced.
本発明の無電解によるＰｄ−Ａｇ合金メッキ膜の製造法
及びそれに使用する無電解メッキ浴についてより詳しく
述べる。The electroless method for producing a Pd-Ag alloy plating film of the present invention and the electroless plating bath used therein will be described in more detail.
本発明において使用される無電解メッキを行うメッキ浴
は、安定な水溶液で構成される。好適な範囲の組成をも
つメッキ浴の構成の仕方を次に示す。The plating bath for electroless plating used in the present invention is composed of a stable aqueous solution. The following describes how to construct a plating bath having a composition within a suitable range.
ａ）パラジウム塩と銀塩とを合せた濃度が０゜００１〜
０．５ｍｏｆ／ｌの所定量のパラジウム塩と銀塩を混合
する。ただし、パラジウム塩に対する銀塩の比率は生成
すべきＰｄ−Ａｇ合金メッキ膜のパラジウム対銀の比率
よりも小さく維持する。a) The combined concentration of palladium salt and silver salt is 0°001~
A predetermined amount of palladium salt and silver salt of 0.5 mof/l are mixed. However, the ratio of silver salt to palladium salt is kept smaller than the ratio of palladium to silver in the Pd-Ag alloy plated film to be produced.
ｂ）０．０１〜５０ｍｏ１／ｌの塩基を加える。b) Add 0.01-50 mol/l of base.
ｃ）０．００１〜１０ｍｏｌ／Ｉｔのキレート剤を加え
て、浴を安定化する。c) Add 0.001-10 mol/It of chelating agent to stabilize the bath.
ｄ）０．０００５〜０．５ｍｏｊ！／ｊ２の還元剤を加
える。d) 0.0005~0.5moj! Add reducing agent /j2.
メッキ浴は、パラジウム及び銀の金属イオン、還元剤の
濃度が高いと、或いはキレート剤、塩基の濃度が低いと
金属塩が自然に還元されて黒い金属粉末を析出する傾向
を有する。また、逆の場合にはメッキ速度が下がり、実
用的でなくなる。When the plating bath has a high concentration of palladium and silver metal ions and a reducing agent, or a low concentration of a chelating agent and a base, the metal salt tends to be naturally reduced and black metal powder is deposited. Moreover, in the opposite case, the plating speed decreases, making it impractical.
本発明で使用するパラジウム塩としては本質的にすべて
の２価パラジウム塩、錯体が使用できる。As the palladium salt used in the present invention, essentially all divalent palladium salts and complexes can be used.
例えばｐａｃｉ！、ｚ、（ＮＨ４）２ ＰｄＣｌ！、、
、Ｐｄ（Ｃ）（ｓｃＯｏ）ｘ、Ｐｄ（ＮＯｓ）ｔ 、
ＰｄＳＯ４等である。銀塩についても、水溶液になり
えるすべての銀塩が使用できる。例えば、Ａ ｇ Ｎ
０２ 、ＡｇｚｓＯ＜ 、ＫＡｇ（ＣＮ）ｚ、Ａｇｌ、
ＡｇＣＮ等である。For example, paci! ,z,(NH4)2PdCl! ,,
, Pd(C)(scOo)x, Pd(NOs)t,
Such as PdSO4. Regarding silver salts, all silver salts that can be made into an aqueous solution can be used. For example, A g N
02, AgzsO< , KAg(CN)z, Agl,
AgCN etc.
メッキ浴中のパラジウム塩と銀塩との比率をパラジウム
対銀のモル比でｌ：工としたときには、銀だけからなる
メッキ膜が生成するようにメッキ浴中のパラジウム塩と
銀塩との比率（パラジウム対銀の比で表わす）と同じ比
率をもつＰｄ−Ａｇ合金メッキ膜が生成されることはな
く、生成するＰｄ−Ａｇ合金メッキ膜のパラジウム対銀
のモル比はずれている。メッキ浴中の（パラジウム十銀
）に対する銀のモル比率と生成するＰｄ−Ａｇ合金メッ
キ膜中のＡｇのモル比率の関係を調べたところ、第１図
に示すような関係にあることが明らかになった。したが
って．メッキ浴中のパラジウム塩に対する銀塩の比率（
パラジウム対銀の比率として表わす）は、生成すべきＰ
ｄ−Ａｇ合金メッキ膜のパラジウム対銀の比率よりも小
さ（する必要がある。When the ratio of palladium salt to silver salt in the plating bath is expressed as the molar ratio of palladium to silver, the ratio of palladium salt to silver salt in the plating bath is set so that a plating film consisting only of silver is generated. A Pd-Ag alloy plating film having the same ratio (expressed as a ratio of palladium to silver) is not produced, and the molar ratio of palladium to silver in the Pd-Ag alloy plating film that is produced is different. When we investigated the relationship between the molar ratio of silver to (10 silver palladium) in the plating bath and the molar ratio of Ag in the Pd-Ag alloy plating film produced, it was found that there was a relationship as shown in Figure 1. became. therefore. The ratio of silver salt to palladium salt in the plating bath (
(expressed as the ratio of palladium to silver) is the P to be produced.
(need to be) smaller than the palladium to silver ratio of the d-Ag alloy plating film.
第１図に見られるようにメッキ浴中のパラジウムに対す
る銀のモル比を大きくすると、Ｐｄ−Ａｇ合金メッキ膜
中の銀の組成割合が増す傾向にある。この関係により０
から１００％までの任意の組成を持つＰｄ−Ａｇ合金メ
ッキ膜を得ることができる。ただし．メッキ浴中のＡｇ
／Ｐｄのモル比と膜中のＡｇ／Ｐｄのモル比の関係につ
いてはメッキ条件、温度、ｐＨ１各添加剤の濃度等で若
干異なるため、各条件毎にその関係を把握する必要があ
る。As seen in FIG. 1, when the molar ratio of silver to palladium in the plating bath is increased, the composition ratio of silver in the Pd-Ag alloy plating film tends to increase. Due to this relationship, 0
It is possible to obtain a Pd-Ag alloy plating film having any composition from 100% to 100%. however. Ag in plating bath
The relationship between the Ag/Pd molar ratio and the Ag/Pd molar ratio in the film differs slightly depending on the plating conditions, temperature, pH 1, concentration of each additive, etc., so it is necessary to understand the relationship for each condition.
メッキ浴の安定性と実用的なメッキ速度を得るためには
パラジウムと銀を合せた濃度が０．００５〜０．０５ｍ
ｏｆ／１であることが好ましい。In order to obtain stability of the plating bath and practical plating speed, the combined concentration of palladium and silver should be 0.005 to 0.05 m
Preferably, it is of/1.
塩基は、パラジウム及び銀の錯体形成、錯体の安定化、
ｐＨ調整のために必要とされ、アンモニア又はアルキル
アミン、エタノールアミン、エチレンジアミン等のアミ
ン化合物が用いられる。これらを一種ないし数種混合す
る。アンモニアを用いる場合、０．５〜５．０ｍｏｆ／
ｊ２が好ましい。Bases are used for complex formation of palladium and silver, stabilization of complexes,
Required for pH adjustment, ammonia or amine compounds such as alkylamines, ethanolamine, ethylenediamine, etc. are used. One or more of these may be mixed. When using ammonia, 0.5 to 5.0 mof/
j2 is preferred.
また．メッキ浴のｐＨは９〜１４とすることが好ましい
。Also. The pH of the plating bath is preferably 9 to 14.
還元剤としては、ヒドラジン又はヒドラジニウム化合物
の少くとも一種を用いる。ヒドラジニウム化合物として
は、例えば硫酸ヒドラジン、塩酸ヒドラジンを用いるこ
とができる。特に、ヒドラジン、硫酸ヒドラジン、塩酸
ヒドラジン等を用いる場合、光沢のあるメッキ膜が安定
して得られる。At least one type of hydrazine or hydrazinium compound is used as the reducing agent. As the hydrazinium compound, for example, hydrazine sulfate or hydrazine hydrochloride can be used. In particular, when hydrazine, hydrazine sulfate, hydrazine hydrochloride, etc. are used, a glossy plating film can be stably obtained.
このとき、０．００３〜０．０５ｍｏｊ２／ｆｆｉの濃
度とするのが好ましい。At this time, it is preferable to set the concentration to 0.003 to 0.05 moj2/ffi.
還元剤は、通常光に金属イオン、塩基、キレート剤等を
含む水溶液を調製後、その水溶液に別に調製した還元剤
の水溶液を入れることにより加えられる。The reducing agent is usually added by preparing an aqueous solution containing metal ions, bases, chelating agents, etc., and then adding a separately prepared aqueous solution of the reducing agent to the aqueous solution.
キレート剤は、パラジウム及び銀イオンを安定化するた
めのものであり．メッキ浴にキレート剤を加えておくこ
とにより、安定した浴が得られる。Chelating agents are used to stabilize palladium and silver ions. By adding a chelating agent to the plating bath, a stable bath can be obtained.
キレート剤としては、アミノ多価酢酸又はその塩の少な
くとも一つが用いられる。その例としては、エチレンジ
アミン四酢酸、エチレンジアミン四酢酸二ナトリウム、
ジエチレントリアミン五酢酸（ＤＴＰＡ）、トリエチレ
ンテトラミン六酢酸（ＴＴＨＡ）等を挙げることができ
、それらを１種ないし数種加える。この時０．０１〜１
．０ｍ ｏ ｌ ／ ｌの濃度が適当である。As the chelating agent, at least one of amino polyacetic acid or a salt thereof is used. Examples include ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetic acid,
Examples include diethylenetriaminepentaacetic acid (DTPA), triethylenetetraminehexaacetic acid (TTHA), and one or more of them may be added. At this time 0.01~1
．． A concentration of 0 mol/l is suitable.
その他、一般の無電解メッキ浴に用いられる改良剤や安
定化剤等の微量の添加剤も利用できる。In addition, trace amounts of additives such as modifiers and stabilizers used in general electroless plating baths can also be used.
本発明による無電解のメッキは触媒活性の担体を先に述
べたメッキ浴中に浸すことにより行う。Electroless plating according to the invention is carried out by immersing the catalytically active support in the plating bath described above.
なお、「触媒活性の担体」とは金属イオンの還元反応を
起す触媒活性を有する担体をいう。触媒活性のない金属
、プラスチック、セラミックス等の担体に無電解メッキ
を行う場合は、あらかじめ触媒活性化処理によりメッキ
したい表面に、Ｐｄ、Ａｕ、Ａｇ等のアノード酸化触媒
を析出又は付着させておけば良く、また粉末、多孔体、
緻密体、繊維等のいずれの状態のものにもメッキするこ
とが可能である。Note that the term "catalytically active carrier" refers to a carrier having a catalytic activity that causes a reduction reaction of metal ions. When performing electroless plating on a carrier such as a metal, plastic, or ceramic that has no catalytic activity, an anode oxidation catalyst such as Pd, Au, or Ag can be precipitated or attached to the surface to be plated by catalytic activation treatment. Good, also powder, porous body,
It is possible to plate objects in any state, such as dense bodies or fibers.
触媒活性化は、通常５ｎＣ１２ｔ ２０〜４０ｇ／ｌ
、ＨＣ１，１０〜２０ｍｆ！、／４２の水溶液とＰｄＣ
Ｌ ｏ、１〜０．５ｇ／ｌ、ＨＣ７２１〜５ｍ ｆｌ
／ ｌの水溶液に交互に担体である物を浸漬すること
に行う。これらの溶液による処理を交互に行うさいは、
１つの溶液の処理後、純水による充分な洗浄を行うのが
適当である。また、Ｓ ｎ Ｃ４２ｚのかわりに５ｎＦ
ｚ水溶液を用いてもよく、またＰｄＣｆ、溶液に加えて
、Ａ ｇ Ｎ Ｏ３溶液への浸漬を行い、ＡｇとＰｄの
両方の核を析出させてもよい。Catalyst activation is usually 5nC12t 20-40g/l
, HC1, 10~20mf! , /42 aqueous solution and PdC
Lo, 1~0.5g/l, HC721~5m fl
/l of the aqueous solution by alternately immersing the carrier. When alternating treatments with these solutions,
After processing one solution, it is appropriate to perform thorough washing with pure water. Also, 5nF instead of S n C42z
z aqueous solution may be used, or in addition to the PdCf solution, immersion may be performed in an A g N O3 solution to precipitate both Ag and Pd nuclei.
メッキはメッキ浴の温度を高めることにより実用的なメ
ッキ速度が得られる。その温度は３０〜８５℃が適当で
あり、８５゛Ｃを越える温度では浴が不安定となり、３
０゛Ｃ未満ではメッキ速度が十分ではない。Practical plating speeds can be achieved by increasing the temperature of the plating bath. The appropriate temperature is 30 to 85°C; if the temperature exceeds 85°C, the bath becomes unstable.
If the temperature is less than 0°C, the plating speed is not sufficient.
メッキ速度は浴の組成、温度、時間により変化するため
、正確には測定できないが、通常１時間当り２〜２０μ
ｍの厚みで膜が形成される。The plating speed varies depending on the bath composition, temperature, and time, so it cannot be measured accurately, but it is usually 2 to 20μ per hour.
A film is formed with a thickness of m.
膜は数百μｍまで厚くしても光沢のある膜を呈している
。Even when the film is thick up to several hundred μm, it remains glossy.
還元剤として次亜リン酸ナトリウムやホウ水素化ナトリ
ウム等を使用する場合は、リンやホウ素が数％含まれる
Ｐｄ−Ａｇ合金膜となるが、本発明によりヒドラジン系
の還元剤を用いる場合には純度の高い合金膜が得られる
。When sodium hypophosphite, sodium borohydride, etc. are used as a reducing agent, the resulting Pd-Ag alloy film contains several percent of phosphorus and boron, but when a hydrazine-based reducing agent is used according to the present invention, An alloy film with high purity can be obtained.
Ｐｄ−Ａｇ合金膜は、単相固溶体であり、Ｘ線回折から
求めた合金の格子定数は、合金組織とともに単調に変化
し、パラジウムと銀の各々の格子定数の中間の値を示し
ている。膜の均質性はＸ線マイクロアナライザーによる
ＰｄとＡｇの面分析の結果からも確認された。The Pd-Ag alloy film is a single-phase solid solution, and the lattice constant of the alloy determined from X-ray diffraction changes monotonically with the alloy structure, showing a value intermediate between the lattice constants of palladium and silver. The homogeneity of the film was also confirmed from the results of surface analysis of Pd and Ag using an X-ray microanalyzer.
メッキ膜は、担体との密着性を高めるために熱処理を行
ってよい。熱処理は１００〜６００℃で行なわれ、不純
物の除去や均質化にも役立つ。The plating film may be heat-treated to improve its adhesion to the carrier. Heat treatment is carried out at 100 to 600°C and also serves to remove impurities and homogenize.
本発明においては、前記のメッキ浴を用いることにより
担体上に無電解メッキが円滑に行われて目的とするＰｄ
−Ａｇ合金メッキ膜がはじめて形成されるようになった
。この無電解メッキによれば、電気メッキでは対応でき
ないような、微細で、複雑な、特に小さい孔の内面にま
でも、均一な厚みのＰｄ−Ａｇ合金メッキを施すことが
可能であり、Ｐｄ−Ａｇ合金メッキ膜の適用範囲を大い
に広げることができる。In the present invention, by using the above-mentioned plating bath, electroless plating can be smoothly performed on the carrier to obtain the target Pd.
-Ag alloy plating film was formed for the first time. According to this electroless plating, it is possible to apply Pd-Ag alloy plating to a uniform thickness even on the inner surface of minute, complicated, and especially small holes that cannot be covered with electroplating. The scope of application of the Ag alloy plating film can be greatly expanded.
Ｐｄ−Ａｇ合金膜は、接点やコネクター等の電子回路部
品として用いられており、また金の代用材料としても有
望であるが、電気メッキにおいても十分実用しうる膜が
得られていないため、本発明により無電解でＰｄ−Ａｇ
合金メッキ膜が製造できるようになったことは、Ｐｄ−
Ａｇ合金メッキ膜の用途を大きく拡げるものと期待され
る。Pd-Ag alloy films are used as electronic circuit components such as contacts and connectors, and are also promising as a substitute material for gold. Electroless Pd-Ag production by invention
The fact that alloy plating films can now be manufactured is due to the fact that Pd-
It is expected that the applications of Ag alloy plating films will be greatly expanded.
〔実施例］ 以下、本発明を実施例により具体的に説明する。〔Example] Hereinafter, the present invention will be specifically explained with reference to Examples.
ただし、本発明はこれらの実施例のみに限定されるもの
ではない。However, the present invention is not limited only to these examples.
実施例１
次の成分
ＰｄＣｆｚ ・２ＨｚＯ，０，０１ｍｏｌ／１２ＡｇＮ
Ｏｓ ０．００３謡０１／！２Ｎａ−
ＥＤＴＡ ０．１ ｔａｏｌ／ＩＴＴＨ
Ａ ０．０３ ｔａｏｌ／ＩＮＨ
ａＯＨ３，Ｏｔａｏｉ！／Ｉｔ
ヒドラジン ０． ０１ ｔａｏｌ／ｌ
。Example 1 The following components PdCfz ・2HzO, 0.01mol/12AgN
Os 0.003 song 01/! 2Na-
EDTA 0.1 towel/ITTH
A 0.03 towel/INH
aOH3, Otaoi! /It Hydrazine 0. 01 towel/l
.
を含有する、温度５０℃のメッキ液にＳ ｎ Ｃｊ！
ｚ／Ｐｄ（１，触媒液で活性化した／１．０．の板を浸
漬したところ、２時間にて厚さ約５μｍの光沢あるメッ
キ膜が付着した。In a plating solution containing S n Cj! at a temperature of 50°C.
When a plate of z/Pd (1./1.0. activated with a catalyst solution) was immersed, a shiny plating film with a thickness of about 5 μm was deposited in 2 hours.
Ｘ線マイクロアナライザーで定量分析を行ったところ、
５５％Ｐｄ−４５％Ａｇの組成であった。When quantitative analysis was performed using an X-ray microanalyzer,
The composition was 55%Pd-45%Ag.
またＸ線回折ではＰｄ−Ａｇ固溶体のブロードな回折ピ
ークが見られた。Further, in X-ray diffraction, a broad diffraction peak of the Pd-Ag solid solution was observed.
実施例２ 次の成分 Ｐｄ（ＮＨｚ）ａｃＬ ’ ＨｚＯＯ。Example 2 next ingredient Pd(NHz)acL HzOO.
ＡｇＮ０． Ｏ。AgN0. O.
ＤＴＰＡ Ｏ。DTPA O.
ＮＨ，ＯＨ１゜ 硫酸ヒドラジン ０゜ ０２ ｍｏｌ／Ｉ。NH,OH1゜ Hydrazine sulfate 0゜ 02 mol/I.
００２ｍｏｊ２／１
２ ｍｏ１／１
０ ｍｏｌ／１２
００５ｍｏｆ ／ ４１！
を含有する、温度７０℃のメッキ液にＳ ｎ Ｃｊ！
！／ Ｐ ｄ Ｃｌ を触媒液で活性化した白金板を浸
漬したところ、１時間で厚さ約４μｍの光沢のあるメッ
キ膜が生成した。その組成は８０％Ｐｄ−２０％Ａｇで
あった。002moj2/1 2 mo1/1 0 mol/12 005mof/41! In a plating solution containing S n Cj! at a temperature of 70°C.
! When a platinum plate activated with /P d Cl in a catalyst solution was immersed, a shiny plating film with a thickness of about 4 μm was formed in 1 hour. Its composition was 80%Pd-20%Ag.
本発明にの製造法によれば、均一な合金組成をもち、密
着性の良いＰｄ−Ａｇ合金メッキ膜をどのような担体の
上にも形成することができるようになった。さらに、そ
の方法は、電気メッキでは対応できないような、微細で
、複雑な特に小さい孔の内面にまでも均一な厚みのＰｄ
−Ａｇ合金メッキ膜を施すことができるので、広い用途
に用いることができる。また、そのメッキは無電解によ
って行われるので、導電性でないセラミックス等の物体
についても行うことができる。According to the manufacturing method of the present invention, a Pd--Ag alloy plating film having a uniform alloy composition and good adhesion can be formed on any carrier. Furthermore, this method can coat even the inner surfaces of minute, complex, and especially small holes that cannot be covered with electroplating.
- Since it can be coated with an Ag alloy plating film, it can be used for a wide range of purposes. Furthermore, since the plating is performed electrolessly, it can be performed on objects such as non-conductive ceramics.
さらに、本発明の無電解メッキ浴は、これを前記のＰｄ
−Ａｇ合金メッキ膜の製造法に用いて前記の特性を有す
るＰｄ−Ａｇ合金メッキ膜を得ることができる。Furthermore, the electroless plating bath of the present invention can be
A Pd--Ag alloy plating film having the above characteristics can be obtained by using the -Ag alloy plating film manufacturing method.
第１図はメッキ浴中の（パラジウム＋銀）に対する銀の
モル比率と生成するＰｄ−Ａｇ合金メッキ膜中の銀のモ
ル比率との関係を表わすグラフを示す。
第 １
図FIG. 1 is a graph showing the relationship between the molar ratio of silver to (palladium+silver) in the plating bath and the molar ratio of silver in the formed Pd-Ag alloy plating film. Figure 1
Claims (5)
の少なくとも一つからなる塩基、ヒドラジン又はヒドラ
ジニウム塩の少なくとも一つからなる還元剤、アミノ多
価酢酸又はその塩の少なくとも一つからなるキレート剤
を含有し、かつパラジウム塩に対する銀塩の比率は生成
すべきＰｄ−Ａｇ合金メッキ膜のパラジウム対銀の比率
より小さく維持したメッキ浴を用いて、触媒活性なる担
体上にＰｄ−Ａｇ合金メッキ膜を析出させることを特徴
とするＰｄ−Ａｇ合金メッキ膜の製造法。1. A base consisting of at least one of palladium salt, silver salt, ammonia or an amine compound, a reducing agent consisting of at least one of hydrazine or hydrazinium salt, and a chelating agent consisting of at least one of amino polyvalent acetic acid or a salt thereof, Depositing a Pd-Ag alloy plating film on a catalytically active support using a plating bath in which the ratio of silver salt to palladium salt is maintained smaller than the ratio of palladium to silver in the Pd-Ag alloy plating film to be produced. A method for producing a Pd-Ag alloy plating film, characterized by:
０．５ｍｏｌ／ｌ、塩基の濃度が０．０１〜５０ｍｏｌ
／ｌ、還元剤の濃度が０．０００５〜０．５ｍｏｌ／ｌ
、キレート剤の濃度が０．００１〜１０ｍｏｌ／ｌであ
るメッキ浴を用いることを特徴とする請求項１記載のＰ
ｄ−Ａｇ合金メッキ膜の製造法。2. The combined concentration of palladium salt and silver salt is 0.001~
0.5 mol/l, base concentration 0.01-50 mol
/l, the concentration of reducing agent is 0.0005-0.5mol/l
P according to claim 1, characterized in that a plating bath in which the concentration of the chelating agent is 0.001 to 10 mol/l is used.
A method for producing a d-Ag alloy plating film.
を特徴とする請求項１又は２記載のＰｄ−Ａｇ合金メッ
キ膜の製造法。3. The method for producing a Pd-Ag alloy plating film according to claim 1 or 2, characterized in that the temperature of the plating bath is in the range of 30°C to 85°C.
の少なくとも一つからなる塩基、ヒドラジン又はヒドラ
ジニウム塩の少なくとも一つからなる還元剤、アミノ多
価酢酸又はその塩の少なくとも一つからなるキレート剤
を含有し、かつパラジウム塩に対する銀塩の比率は生成
すべきＰｄ−Ａｇ合金メッキ膜のパラジウム対銀の比率
より小さく維持したことを特徴とするＰｄ−Ａｇ合金メ
ッキ用無電解メッキ浴。4. A base consisting of at least one of palladium salt, silver salt, ammonia or an amine compound, a reducing agent consisting of at least one of hydrazine or hydrazinium salt, and a chelating agent consisting of at least one of amino polyvalent acetic acid or a salt thereof, An electroless plating bath for Pd-Ag alloy plating, characterized in that the ratio of silver salt to palladium salt is maintained smaller than the ratio of palladium to silver in the Pd-Ag alloy plating film to be produced.
．５ｍｏｌ／ｌ、塩基の濃度が０．０１〜５０ｍｏｌ／
ｌ、還元剤の濃度が０．０００５〜０．５ｍｏｌ／ｌ、
キレート剤の濃度が０．０００１〜１０ｍｏｌ／ｌであ
ることを特徴とする請求項４記載のＰｄ−Ａｇ合金メッ
キ用無電解メッキ浴。5. The combined concentration of palladium salt and silver salt is 0.01 to 0.
．． 5 mol/l, base concentration 0.01-50 mol/l
l, the concentration of the reducing agent is 0.0005 to 0.5 mol/l,
5. The electroless plating bath for Pd-Ag alloy plating according to claim 4, wherein the concentration of the chelating agent is 0.0001 to 10 mol/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8745890A JPH03287781A (en) | 1990-04-03 | 1990-04-03 | Production of pd-ag alloy plating film by electroless plating and electroless plating bath used therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8745890A JPH03287781A (en) | 1990-04-03 | 1990-04-03 | Production of pd-ag alloy plating film by electroless plating and electroless plating bath used therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03287781A true JPH03287781A (en) | 1991-12-18 |
Family
ID=13915429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8745890A Pending JPH03287781A (en) | 1990-04-03 | 1990-04-03 | Production of pd-ag alloy plating film by electroless plating and electroless plating bath used therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03287781A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185308A (en) * | 2008-02-01 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | HYDROGEN SEPARATING THIN FILM BY SIMULTANEOUS PLATING OF Pd-Ag, AND ITS MANUFACTURING METHOD |
| CN113005438A (en) * | 2021-02-23 | 2021-06-22 | 广东工业大学 | Method for using silver ion accelerator as additive for improving palladium plating rate in chemical palladium plating solution |
-
1990
- 1990-04-03 JP JP8745890A patent/JPH03287781A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009185308A (en) * | 2008-02-01 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | HYDROGEN SEPARATING THIN FILM BY SIMULTANEOUS PLATING OF Pd-Ag, AND ITS MANUFACTURING METHOD |
| CN113005438A (en) * | 2021-02-23 | 2021-06-22 | 广东工业大学 | Method for using silver ion accelerator as additive for improving palladium plating rate in chemical palladium plating solution |
| CN113005438B (en) * | 2021-02-23 | 2023-08-22 | 广东工业大学 | Method for using silver ion accelerator as additive for improving palladium plating rate in chemical palladium plating solution |
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