TWI572742B - Reduction Electroless Silver Plating Solution and Reduced Electroless Silver Plating Method - Google Patents

Reduction Electroless Silver Plating Solution and Reduced Electroless Silver Plating Method Download PDF

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TWI572742B
TWI572742B TW101138421A TW101138421A TWI572742B TW I572742 B TWI572742 B TW I572742B TW 101138421 A TW101138421 A TW 101138421A TW 101138421 A TW101138421 A TW 101138421A TW I572742 B TWI572742 B TW I572742B
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silver
plating solution
plating
cyanide
silver plating
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TW101138421A
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TW201331413A (en
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Daisuke Hashimoto
Kota Kitajima
Akira Okada
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C Uyemura & Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal

Description

還原型無電解鍍銀液及還原型無電解鍍銀方法 Reduced electroless silver plating solution and reduced electroless silver plating method

本發明關於還原型無電解鍍銀液及還原型無電解鍍銀方法，更詳細地，關於液安定，不將基底金屬等過度地粗化，可形成良好的鍍敷皮膜之還原型無電解鍍銀液及使用該鍍銀液之還原型無電解鍍銀方法。 The present invention relates to a reduced electroless silver plating solution and a reduced-type electroless silver plating method. More specifically, regarding liquid stabilization, a reduction-type electroless plating which can form a good plating film without excessively roughening a base metal or the like Silver liquid and reduced electroless silver plating method using the silver plating liquid.

本申請案係以在日本於2011年10月27日申請的日本發明專利申請號碼特願2011-235559為基礎，主張優先權，藉由參照該申請案，而在本申請案中援用。 The present application claims priority based on Japanese Patent Application No. 2011-235559, filed on Jan.

鍍銀係古早使用於裝飾用等，近年來活用其電特性或高反射率，在電工業或光學工業領域、其它電磁波屏蔽或滅菌塗覆等之領域中，亦被多使用。其中，無電解鍍銀係膜厚的控制為可能，在可容易形成必要的膜厚之鍍敷皮膜之點中被多使用。 The silver plating system has been used for decoration and the like in recent years, and in recent years, its electrical characteristics or high reflectance have been utilized, and it has been widely used in the fields of the electric industry or the optical industry, other electromagnetic wave shielding or sterilization coating. Among them, the control of the electroless silver plating film thickness is possible, and it is often used in the point that the plating film having a necessary film thickness can be easily formed.

無電解鍍銀係大致分類為取代型與還原型。取代型的無電解鍍銀係鍍液比較安定性優異，在市場上亦被多利用(例如專利文獻1及2參照)。然而，取代型無電解鍍銀，由於是藉由與質地金屬的取代反應而使鍍銀析出，故有在基底質地具有限制之問題。 Electroless silver plating is roughly classified into a substituted type and a reduced type. The substitution type electroless silver plating type plating solution is excellent in stability and is also widely used in the market (for example, refer to Patent Documents 1 and 2). However, in the substitution type electroless silver plating, since silver plating is precipitated by a substitution reaction with a texture metal, there is a problem in that the texture of the substrate is limited.

另一方面，還原型的無電解鍍銀，係藉由在鍍液中含有還原劑，將水溶性銀化合物還原成金屬銀，使鍍銀析出在基底金屬上者，不粗化基底質地，而且不限制基底質地 的種類，可形成良好的鍍銀皮膜。 On the other hand, the reduced type electroless silver plating is obtained by reducing the water-soluble silver compound to metallic silver by containing a reducing agent in the plating solution, and depositing silver plating on the base metal without coarsening the base texture. Does not limit the texture of the substrate The type can form a good silver plating film.

於還原型的無電解鍍銀液中，尤其從液之安定性的觀點來看，含有氰化銀鉀等的氰化銀化合物作為水溶性銀鹽。使用此氰化銀化合物作為水溶性銀鹽時，一般地相對於銀而言，在鍍液中含有以莫耳比計2倍以上的氰。 In the reduction type electroless silver plating solution, a silver cyanide compound containing potassium silver cyanide or the like is used as a water-soluble silver salt, in particular, from the viewpoint of stability of the liquid. When such a silver cyanide compound is used as the water-soluble silver salt, cyanide which is twice or more the molar ratio is generally contained in the plating solution with respect to silver.

又，於還原型的無電解鍍銀液中，亦有提案藉由添加氰化鉀等的氰化合物，而提高液的安定性之方法，形成在鍍液中游離氰多存在之狀態(例如專利文獻3及非專利文獻1)。 Further, in the reduction type electroless silver plating solution, there is also a proposal to increase the stability of the liquid by adding a cyanide compound such as potassium cyanide to form a state in which free cyanide is present in the plating solution (for example, a patent) Document 3 and Non-Patent Document 1).

然而，此等在以往鍍液中存在之過剩的氰，雖然如上述地可抑制鍍液中的銀之分解而提高安定性，但例如會使由鎳或銅所構成的金屬等之被鍍物溶解而過度粗化其表面，無法形成具有良好的皮膜特性之鍍敷皮膜。 However, in the above-described conventionally, the cyanide which is present in the plating solution can suppress the decomposition of silver in the plating solution and improve the stability, but for example, a metal such as nickel or copper can be plated. It dissolves and excessively roughens the surface, and it is impossible to form a plating film having good film properties.

另一方面，近幾年亦有提案無氰的還原型無電解鍍銀液(例如專利文獻4及5)。然而，於如此的無氰之無電解鍍銀液中，由於氰不存在於鍍液中，雖然不會使基底金屬等溶解而過度粗化表面，但與含氰的鍍液相比，液安定性係顯著差。例如，如專利文獻4及5中記載，亦有提案於無氰的鍍銀液中，藉由添加添加劑而使安定性提高之技術，但尚未具有充分的安定性。再者，於如此之無氰的無電解鍍銀中，隨著膜厚的增厚而成為帶黃色的銀皮膜，在鍍敷皮膜的外觀之點亦有問題。 On the other hand, in recent years, a reduction-type electroless silver plating solution having no cyanide has been proposed (for example, Patent Documents 4 and 5). However, in such a cyanide-free electroless silver plating solution, since cyanide is not present in the plating solution, the surface is excessively roughened without dissolving the base metal or the like, but the liquid is stable compared with the cyanide-containing plating solution. The sexual system is significantly worse. For example, as disclosed in Patent Documents 4 and 5, there is also a proposal to improve the stability by adding an additive to a silver-free silver plating solution, but it has not yet provided sufficient stability. Further, in such a cyanide-free electroless silver plating, a yellowish silver film is formed as the film thickness is increased, and there is a problem in the appearance of the plating film.

〔先前技術文獻〕 [Previous Technical Literature] 〔專利文獻〕 [Patent Document]

〔專利文獻1〕特開2000-309875號公報 [Patent Document 1] JP-A-2000-309875

〔專利文獻2〕特開2002-180259號公報 [Patent Document 2] JP-A-2002-180259

［專利文獻3〕特開平5-279863號公報 [Patent Document 3] Japanese Patent Publication No. Hei 5-279863

〔專利文獻4〕特許3937373號公報 [Patent Document 4] License No. 3937373

〔專利文獻5〕特開2003-268558號公報 [Patent Document 5] JP-A-2003-268558

〔非專利文獻〕 [Non-patent literature]

〔非專利文獻1〕 [Non-Patent Document 1]

「無電解鍍敷 基礎與應用」電鍍金研究會編 日刊工業報社刊p176-177 "Electroless Plating Foundation and Application" Electroplating Gold Research Association, Nikkan Industrial News, p176-177

因此，本發明係鑒於如上述以往之實情而完成者，目的在於提供可防止鍍液中的銀之分解而維持安定性，同時防止鍍敷基底的金屬等被過度地粗化，可形成具有良好的皮膜特性，外觀亦良好的鍍敷皮膜之還原型無電解鍍銀液及使用此鍍銀液之還原型無電解鍍銀方法。 Therefore, the present invention has been made in view of the above-described conventional circumstances, and it is an object of the present invention to provide a product which can prevent the decomposition of silver in a plating solution and maintain stability, and prevent the metal or the like of the plating substrate from being excessively roughened. The reduced-type electroless silver plating solution of the coating film and the reduction type electroless silver plating method using the silver plating liquid.

本發明者們為了解決上述目的，重複專心致力的檢討，結果發現藉由控制鍍液中的氰濃度，而維持鍍液的安定性，防止基底金屬等被過度粗化，可形成具有良好的皮膜特性，外觀亦優異之鍍敷皮膜，而完成本發明。 In order to solve the above-mentioned problems, the inventors of the present invention have repeatedly conducted intensive review, and found that by controlling the concentration of cyanide in the plating solution, the stability of the plating solution is maintained, and the base metal or the like is prevented from being excessively roughened, and a good film can be formed. The present invention has been completed by a plating film which is excellent in characteristics and appearance.

即，本發明的還原型無電解鍍銀液係含有水溶性銀鹽 與還原劑之還原型無電解鍍銀液，其係含有0.006×10-3mol/L~12.5×10-3mol/L的氰化物離子。 That is, the reduced electroless silver plating liquid of the present invention contains a reduced-type electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and contains 0.006×10 -3 mol/L to 12.5×10 -3 mol/L. Cyanide ion.

又，本發明的還原型無電解鍍銀液，較佳為上述水溶性銀鹽係氰化合物以外之銀鹽，上述氰化物離子作為鹼金屬氰化物含有。 Further, the reduced electroless silver plating solution of the present invention is preferably a silver salt other than the water-soluble silver salt-based cyanide compound, and the cyanide ion is contained as an alkali metal cyanide.

另外，本發明的還原型無電解鍍銀液，較佳為上述還原劑係由硫酸羥基銨、醋酸羥基銨中選出的1種以上者。 Further, in the reduced electroless silver plating solution of the present invention, the reducing agent is preferably one or more selected from the group consisting of ammonium hydroxysulfate and ammonium hydroxyacetate.

還有，本發明的還原型無電解鍍銀液較佳為pH係8~11者。 Further, the reduced electroless silver plating solution of the present invention is preferably a pH system of 8 to 11.

又，本發明的還原型無電解鍍銀方法，係使用含有0.006×10-3mol/L~12.5×10-3mol/L的氰化物離子之還原型無電解鍍銀液，其為含有水溶性銀鹽與還原劑之還原型無電解鍍銀液，對被鍍物施予無電解鍍銀。 Further, the reduced electroless silver plating method of the present invention uses a reduced type electroless silver plating liquid containing cyanide ions of 0.006 × 10 -3 mol / L to 12.5 × 10 -3 mol / L, which is water-soluble. A reduced-type electroless silver plating solution of a silver salt and a reducing agent, and electroless silver plating is applied to the object to be plated.

依照本發明的還原型無電解鍍銀液及還原型無電解鍍銀方法，可防止鍍液中的銀之分解而使液之安定性成為良好，防止成為鍍敷之基底的金屬等之被鍍物被過度地粗化，可形成具有良好的皮膜特性，外觀亦優異之鍍敷皮膜。 According to the reduced electroless silver plating solution and the reduced electroless silver plating method of the present invention, it is possible to prevent the decomposition of silver in the plating solution and to improve the stability of the liquid, and to prevent the plating of the metal or the like which is the base of the plating. The material is excessively roughened, and a plating film having excellent film properties and excellent appearance can be formed.

〔實施發明的形態〕 [Formation of the Invention]

以下，詳細說明本發明的還原型無電解鍍銀液之具體 的實施形態(以下稱為「本實施形態」)。 Hereinafter, the specifics of the reduced electroless silver plating solution of the present invention will be described in detail. The embodiment (hereinafter referred to as "this embodiment").

本實施形態的還原型無電解鍍銀液，係含有水溶性銀鹽與還原劑之還原型無電解鍍銀液，藉由還原劑將水溶性銀鹽還原成金屬銀，藉由使鍍銀析出在基底金屬等的被鍍物上，而形成鍍銀皮膜。 The reduced electroless silver plating solution of the present embodiment is a reduced-type electroless silver plating liquid containing a water-soluble silver salt and a reducing agent, and the water-soluble silver salt is reduced to metallic silver by a reducing agent, and silver plating is precipitated. A silver plating film is formed on the object to be plated such as a base metal.

而且，本實施形態的還原型無電解鍍銀液之特徵為在含有水溶性銀鹽與還原劑之鍍液中，含有經調製成規定的濃度範圍之氰化物離子。具體地，含有0.006×10-3mol/L~12.5×10-3mol/L的氰化物離子。 Further, the reduced electroless silver plating solution of the present embodiment is characterized in that a plating solution containing a water-soluble silver salt and a reducing agent contains cyanide ions which are prepared to have a predetermined concentration range. Specifically, it contains 0.006 × 10 -3 mol/L to 12.5 × 10 -3 mol/L of cyanide ions.

以往，於添加有氰化銀鉀等的水溶性銀鹽或氰化鉀等的氰化合物作為添加劑之還原型無電解鍍銀液中，雖然液的安定性優異，但例如過剩地溶解由銅或鎳等所成之鍍敷基底的金屬等而粗化，無法形成具有良好的皮膜特性之鍍敷皮膜。 In the reduction type electroless silver plating liquid to which a cyano compound such as a water-soluble silver salt such as potassium silver cyanide or potassium cyanide is added as an additive, the stability of the liquid is excellent, but for example, it is excessively dissolved by copper or The metal or the like of the plating base formed of nickel or the like is roughened, and a plating film having good film properties cannot be formed.

另一方面，為了避免對基底金屬等之過剩的溶解，亦開發無氰的鍍液，但尤其在液的安定性低之鍍銀液中，由於無氰而鍍液中的銀之分解快速地發生，顯著損害鍍液的安定性。又，於如此的無氰之鍍液中，形成帶有黃色調的鍍敷皮膜，無法形成具有良好的外觀之鍍敷皮膜。如此的外觀不良之鍍銀皮膜，例如當對於LED裝置使用時，亦導致反射率之降低。 On the other hand, in order to avoid excessive dissolution of the base metal or the like, a cyanide-free plating solution is also developed, but in particular, in the silver plating liquid having low liquid stability, the decomposition of silver in the plating solution is fast due to the absence of cyanide. Occurs, significantly impairing the stability of the bath. Further, in such a cyanide-free plating solution, a plating film having a yellow hue is formed, and a plating film having a good appearance cannot be formed. Such a poorly-performed silver-plated film, for example, when used with an LED device, also causes a decrease in reflectance.

相對於其，本實施形態的還原型無電解鍍銀液，係在鍍液中含有0.006×10-3mol/L~12.5×10-3mol/L的氰化物離子。 The reduced electroless silver plating solution of the present embodiment contains 0.006 × 10 -3 mol/L to 12.5 × 10 -3 mol/L of cyanide ions in the plating solution.

藉由如此的還原型無電解鍍銀液，不僅得到以往使用氰化合物的無電解鍍銀液與無氰的無電解鍍銀液這兩者之優點，而且液的安定性高，不過度地粗化基底金屬等的被鍍物，可形成皮膜特性優異之鍍敷皮膜。又，藉由此還原型無電解鍍銀液，得到漂亮的白色銀之鍍敷皮膜，具有良好的外觀，例如當採用於LED裝置時，可提高反射特性。 According to such a reduced electroless silver plating solution, not only the advantages of both the electroless silver plating liquid using the cyanide compound and the electroless silver plating liquid without cyanide are obtained, and the stability of the liquid is high, and the liquid is not excessively coarse. A plated material such as a base metal can be formed to form a plating film having excellent film properties. Further, by using the reduced-type electroless silver plating solution, a beautiful white silver plating film is obtained, which has a good appearance, and when used in an LED device, for example, the reflection characteristics can be improved.

此處，當氰化物離子的含量未達0.006×10-3mol/L時，鍍液中的銀會分解，液的安定性變差。又，隨著鍍敷皮膜增厚，皮膜變成帶黃色，無法形成具有良好的外觀之鍍敷皮膜。另一方面，當含量多於12.5×10-3mol/L時，由於鍍液中存在的氰，會溶解由成為鍍敷基底的金屬等所成之被鍍物及過剩地粗化，即使在該被鍍物上形成鍍敷皮膜，也得不到具有良好的皮膜特性之鍍敷皮膜。 Here, when the content of the cyanide ion is less than 0.006 × 10 -3 mol/L, the silver in the plating solution is decomposed, and the stability of the liquid is deteriorated. Further, as the plating film is thickened, the film becomes yellowish, and a plating film having a good appearance cannot be formed. On the other hand, when the content is more than 12.5 × 10 -3 mol/L, the cyanide present in the plating solution dissolves the object to be plated, which is a metal such as a plating base, and excessively coarsens, even in the case of A plating film is formed on the object to be plated, and a plating film having good film properties is not obtained.

氰化物離子源係沒有特別的限定，例如可使用氰化鉀或氰化鈉等的鹼金屬氰化物。又，可使用氰化銀鉀等的氰化銀化合物作為水溶性銀鹽，使用此作為氰化物離子源的一部分或全部，以上述含量使含有。 The cyanide ion source system is not particularly limited, and for example, an alkali metal cyanide such as potassium cyanide or sodium cyanide can be used. Further, a silver cyanide compound such as potassium silver cyanide may be used as the water-soluble silver salt, and a part or all of the cyanide ion source may be used as the above content.

於此等的氰化物離子源之中，尤其更佳為使用鹼金屬氰化物。藉由使用鹼金屬氰化物，可恰當且簡便地將氰化物離子濃度調製成上述濃度範圍，可更有效率且有效果地維持液的安定性而形成皮膜特性良好之鍍敷皮膜。又，即使連續使用時，也不需要隨時添加，而且也沒有如作為氰化銀化合物添加時鍍液中銀量增加而損害安定性者。 Among these cyanide ion sources, it is more preferable to use an alkali metal cyanide. By using an alkali metal cyanide, the cyanide ion concentration can be appropriately and easily adjusted to the above concentration range, and the stability of the liquid can be maintained more efficiently and effectively to form a plating film having excellent film properties. Further, even if it is used continuously, it is not necessary to add it at any time, and there is no increase in the amount of silver in the plating solution when it is added as a silver cyanide compound to impair stability.

於本實施形態的還原型無電解鍍銀液中，作為水溶性銀鹽，只要可溶於鍍液中，則沒有特別的限定，例如可使用硝酸銀、氧化銀、硫酸銀、氯化銀、亞硫酸銀、碳酸銀、醋酸銀、乳酸銀、磺基琥珀酸銀、磺酸銀、胺磺酸銀、草酸銀等。又，作為水溶性銀鹽，如上述，亦可使用氰化銀鉀等的氰化銀化合物。此等水溶性銀鹽係可為單獨1種或併用2種以上。 In the reduced-type electroless silver plating solution of the present embodiment, the water-soluble silver salt is not particularly limited as long as it is soluble in the plating solution, and for example, silver nitrate, silver oxide, silver sulfate, silver chloride, or the like can be used. Silver sulfate, silver carbonate, silver acetate, silver lactate, silver sulfosuccinate, silver sulfonate, silver amine sulfonate, silver oxalate, and the like. Further, as the water-soluble silver salt, a silver cyanide compound such as potassium silver cyanide may be used as described above. These water-soluble silver salts may be used alone or in combination of two or more.

水溶性銀鹽的含量以銀濃度計，較佳為0.1g/L~10g/L(0.9×10-3mol/L~/90×10-3mol/L)，更佳為0.1g/L~3.0g/L(0.9×10-3mol/L~30×10-3mol/L)。藉由使水溶性銀鹽的含量以銀濃度計成為0.1g/L~10g/L之範圍，可使鍍銀的析出速度變良好，而且成為安定性高之鍍液。 The content of the water-soluble silver salt is preferably 0.1 g/L to 10 g/L (0.9×10 -3 mol/L to 90×10 -3 mol/L), more preferably 0.1 g/L, in terms of silver concentration. ~3.0g/L (0.9×10 -3 mol/L~30×10 -3 mol/L). When the content of the water-soluble silver salt is in the range of 0.1 g/L to 10 g/L in terms of the silver concentration, the deposition rate of silver plating can be improved, and the plating solution having high stability can be obtained.

又，使用氰化銀化合物作為水溶性銀鹽時，所添加的氰化銀化合物或該氰化銀化合物與作為添加劑含有的氰化合物之含量，係以上述氰化物離子濃度的範圍含有，即以0.006×10-3mol/L~12.5×10-3mol/L含有。 Further, when a silver cyanide compound is used as the water-soluble silver salt, the content of the silver cyanide compound or the silver cyanide compound and the cyano compound contained as an additive is contained in the range of the cyanide ion concentration, that is, 0.006 × 10 -3 mol / L ~ 12.5 × 10 -3 mol / L.

作為還原劑，只要是具有將鍍液中的水溶性銀鹽還原成金屬銀之能力者，而且為水溶性之化合物，則沒有特別的限定，可使用例如肼及其衍生物、甲醛化合物、羥基銨鹽、糖類、羅謝爾(Rochelle)鹽、氫化硼化合物、次磷酸鹽、DMAB(二甲基胺硼烷)、抗壞血酸等。此等還原劑係可為單獨1種或併用2種以上。 The reducing agent is not particularly limited as long as it has a function of reducing the water-soluble silver salt in the plating solution to metallic silver, and is a water-soluble compound, and for example, hydrazine and its derivatives, formaldehyde compounds, and hydroxyl groups can be used. Ammonium salts, sugars, Rochelle salts, boron hydride compounds, hypophosphites, DMAB (dimethylamine borane), ascorbic acid, and the like. These reducing agents may be used alone or in combination of two or more.

於此等的還原劑之中，特佳為使用硫酸羥基銨、醋酸羥基銨等的羥基銨鹽。其理由係因為藉由此等的還原劑， 控制鍍敷時間，而可容易改變膜厚，進行增厚處理等，可容易形成由所欲的膜厚所構成，具有良好的皮膜特性之鍍敷皮膜。 Among these reducing agents, a hydroxylammonium salt such as ammonium hydroxysulfate or ammonium hydroxyacetate is particularly preferably used. The reason is because of the reducing agent, etc. By controlling the plating time, the film thickness can be easily changed, and a thickening treatment or the like can be performed, and a plating film having a desired film thickness and having excellent film properties can be easily formed.

若更具體地說明，則在本實施的還原型無電解鍍銀液中，如上述地，以不過剩地溶解基底金屬等為目的，將氰化物離子控制在規定的濃度範圍。因此，當使用還原力較強的DMAB等之還原劑時，於鍍液中有發生銀的分解之可能性。該點係藉由使用硫酸羥基銨或醋酸羥基銨等的羥基銨鹽，而防止鍍液中銀的分解，使安定地發生還原反應。 More specifically, in the reduced electroless silver plating solution of the present embodiment, the cyanide ions are controlled to a predetermined concentration range for the purpose of dissolving the base metal or the like excessively as described above. Therefore, when a reducing agent such as DMAB having a strong reducing power is used, there is a possibility that decomposition of silver occurs in the plating solution. This point is to prevent the decomposition of silver in the plating solution by using a hydroxyammonium salt such as ammonium hydroxysulfate or hydroxyammonium acetate, and to carry out a reduction reaction in a stable manner.

又，當使用肼或甲醛等之還原力較弱的還原劑時，由於銀的析出速度變慢，在基底金屬等的表面中，銀不析出的部分係變長時間存在，鍍液中的氰係在該部分作用，有過度溶解之可能性。此點亦藉由使用硫酸羥基銨或醋酸羥基銨等之羥基胺類，而不使基底金屬等溶解，可確實地藉由還原反應來析出鍍銀，故藉由鍍敷時間的控制，可使所欲膜厚的鍍銀被覆於基底金屬等，可形成具有良好的皮膜特性之鍍敷皮膜。 In addition, when a reducing agent having a weak reducing power such as hydrazine or formaldehyde is used, since the precipitation rate of silver is slow, a portion where silver does not precipitate on the surface of the base metal or the like is present for a long period of time, and cyanide in the plating solution is present. It works in this part and has the possibility of excessive dissolution. In this case, by using a hydroxylamine such as ammonium hydroxysulfate or hydroxyammonium acetate, the base metal or the like is not dissolved, and silver plating can be surely precipitated by a reduction reaction, so that the plating time can be controlled. The silver plating of the desired film thickness is coated on the base metal or the like to form a plating film having good film properties.

如此地，藉由硫酸羥基銨或醋酸羥基銨，可容易形成所欲膜厚的鍍敷皮膜，同時使液的安定性更優異，可防止因氰而過剩地溶解基底金屬等，更有效果地形成皮膜特性為良好的鍍敷皮膜。 In this way, by using ammonium hydroxysulfate or hydroxyammonium acetate, a plating film having a desired film thickness can be easily formed, and the stability of the liquid can be further improved, and the base metal can be prevented from being excessively dissolved by cyanide, and the effect is more effective. The coating film is formed into a good plating film.

還原劑之含量例如較佳為0.006mol/L~0.12mol/L，更佳為0.006mol/L~0.03mol/L。還原劑的含量比0.006mol/L少時，無法將鍍液中的水溶性銀鹽還原成金屬 銀，有無法使鍍銀充分析出之可能性。另一方面，比0.12mol/L還多時，有對鍍液的安定性造成不利影響之可能性，同時在經濟上亦不宜。 The content of the reducing agent is, for example, preferably from 0.006 mol/L to 0.12 mol/L, more preferably from 0.006 mol/L to 0.03 mol/L. When the content of the reducing agent is less than 0.006 mol/L, the water-soluble silver salt in the plating solution cannot be reduced to metal. Silver, there is a possibility that the silver plating cannot be analyzed. On the other hand, when it is more than 0.12 mol/L, there is a possibility that the stability of the plating solution is adversely affected, and it is also economically unsuitable.

本實施形態的還原型無電解鍍銀液，係液溫可使用0~80℃之範圍，特別地藉由使用30~60℃左右，可使鍍液的安定性更進一步地良好。鍍液的溫度若過低，則銀的析出速度慢，為了得到規定的銀析出量，需要長時間。另一方面，鍍液的溫度若過高，則容易引起因自分解反應所致的還原劑之損失，或鍍液安定性之降低。 In the reduced electroless silver plating solution of the present embodiment, the liquid temperature can be used in the range of 0 to 80 ° C, and particularly, the stability of the plating solution can be further improved by using about 30 to 60 ° C. If the temperature of the plating solution is too low, the precipitation rate of silver is slow, and it takes a long time to obtain a predetermined amount of silver deposition. On the other hand, if the temperature of the plating solution is too high, the loss of the reducing agent due to the self-decomposition reaction is likely to occur, or the stability of the plating solution is lowered.

又，還原型無電解鍍銀液的pH係可以2~14之範圍使用，但從如上述地含有規定濃度的氰化物離子者來看，pH特佳為8~11之範圍。藉由使鍍液的pH成為8以上，而有效果地抑制氰氣的發生，不對環境造成不良影響，可安全地使用。另外，可使鍍液的安定性更進一步地良好。還有，藉由使pH成為11以下，可使鍍液的安定性及鍍敷皮膜的皮膜特性更進一步地良好。 Further, the pH of the reduced electroless silver plating solution can be used in the range of 2 to 14, but the pH is particularly preferably in the range of 8 to 11 from the viewpoint of containing cyanide ions having a predetermined concentration as described above. By setting the pH of the plating solution to 8 or more, it is effective to suppress the occurrence of cyanide gas, and it is safe to use without adversely affecting the environment. In addition, the stability of the plating solution can be further improved. Further, by setting the pH to 11 or less, the stability of the plating solution and the film properties of the plating film can be further improved.

鍍液的pH調整，通常於降低pH的情況中，使用具有與水溶性銀鹽的陰離子部分同種之陰離子部分的酸，例如當使用硫酸銀作為水溶性銀鹽時，使用硫酸進行，當使用硝酸銀作為水溶性銀鹽時，使用硝酸進行。另一方面，於升高pH的情況中，使用氫氧化鈉等的鹼金屬氫氧化物、氨等進行。 The pH of the plating solution is adjusted, usually in the case of lowering the pH, using an acid having the same anionic portion as the anionic portion of the water-soluble silver salt, for example, when silver sulfate is used as the water-soluble silver salt, using sulfuric acid, when silver nitrate is used. As a water-soluble silver salt, it is carried out using nitric acid. On the other hand, in the case of raising the pH, it is carried out using an alkali metal hydroxide such as sodium hydroxide, ammonia or the like.

又，於本實施形態的還原型無電解鍍銀液中，視需要可添加錯化劑。錯化劑係沒有特別的限定，可使用亞硫酸 鹽、琥珀醯亞胺、乙內醯脲衍生物、乙二胺、乙二胺四乙酸(EDTA)等。此等錯化劑係可為單獨1種或併用2種以上。 Further, in the reduced electroless silver plating solution of the present embodiment, a distoring agent may be added as needed. The stabilizing agent is not particularly limited, and sulfurous acid can be used. Salt, amber imine, carbendazole derivative, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), and the like. These distorting agents may be used alone or in combination of two or more.

錯化劑的添加量亦隨著其種類而不同，沒有特別的限定，但較佳為1g/L~100g/L左右。藉由使錯化劑的濃度成為如此的範圍，可使鍍銀的析出速度成為良好，而且可成為安定性更進一步地優異之鍍液。 The amount of the distoring agent to be added varies depending on the type thereof, and is not particularly limited, but is preferably about 1 g/L to 100 g/L. By setting the concentration of the trouble-solving agent to such a range, the deposition rate of silver plating can be made good, and the plating solution which is further excellent in stability can be obtained.

另外，視需要亦可添加眾所周知的界面活性劑、pH調整劑、緩衝劑、平滑劑、應力緩和劑等之添加劑。 Further, additives such as well-known surfactants, pH adjusters, buffers, smoothing agents, stress relieving agents, and the like may be added as needed.

使用具有上述特徵的還原型無電解鍍銀液之鍍敷方法，例如藉由在經調節至上述液溫及pH值的還原型無電解鍍銀液中，浸漬被鍍物而施予鍍銀。又，亦可藉由對被鍍物，將還原型無電解鍍銀液等噴霧、塗佈等，而使鍍液接觸被鍍物，進行鍍敷處理。 The plating method of the reduced electroless silver plating liquid having the above characteristics is applied, for example, by immersing the object to be plated in a reduced-type electroless silver plating liquid adjusted to the above liquid temperature and pH, and silver plating is applied. In addition, by spraying, coating, or the like on the object to be plated, the plating solution may be brought into contact with the object to be plated and subjected to a plating treatment.

此無電解鍍銀方法係如上述，主要藉由鍍液中所含有的還原劑，將水溶性銀鹽還原成金屬銀，在成為鍍敷基底的金屬等之被鍍物上，使鍍銀析出而形成鍍敷皮膜。 As described above, the electroless silver plating method mainly reduces the water-soluble silver salt to metallic silver by a reducing agent contained in the plating solution, and deposits silver plating on the object to be plated such as a metal which is a plating base. A plating film is formed.

形成無電解鍍銀皮膜的被鍍物，係沒有特別的限定，對於銅或鎳等的金屬材料或其它各種的導電性材料、非導電性材料等可適用。以金屬材料作為被鍍物時，在依照常見方法進行脫脂處理等的前處理後，將被鍍物直接浸漬在鍍液中。 The object to be plated which forms the electroless silver plating film is not particularly limited, and is applicable to metal materials such as copper or nickel, various other conductive materials, non-conductive materials, and the like. When a metal material is used as the object to be plated, the object to be plated is directly immersed in the plating solution after pretreatment such as degreasing treatment according to a usual method.

又，對於陶瓷、塑膠等的非金屬材料進行鍍敷處理時，係在進行脫脂處理等的前處理後，將被鍍物予以活化 處理，然後浸漬於鍍液中。活化處理只要依照常見方法即可，例如使用鈀觸媒(觸媒-加速劑法、敏化-活化劑法等)、銀觸媒、銅觸媒等，依照眾所周知的條件，進行活化處理。 In addition, when a non-metallic material such as ceramics or plastic is subjected to a plating treatment, the object to be plated is activated after pre-treatment such as degreasing treatment. It is then immersed in the bath. The activation treatment may be carried out according to a usual method, for example, using a palladium catalyst (catalyst-accelerator method, sensitizer-activator method, etc.), a silver catalyst, a copper catalyst, or the like, and performing activation treatment in accordance with well-known conditions.

如以上，本實施形態的還原型無電解鍍銀液，係含有水溶性銀鹽與還原劑之還原型無電解鍍銀液，其係含有0.006×10-3mol/L~12.5×10-3mol/L的氰化物離子。藉由如此的還原型無電解鍍銀液，有效果地防止鍍銀液中的銀之分解而使液的安定性變良好，防止基底金屬等的被鍍物被過度地粗化，可形成具有良好的皮膜特性，外觀亦優異之鍍敷皮膜。 As described above, the reduced electroless silver plating solution of the present embodiment is a reduced-type electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and contains 0.006 × 10 -3 mol/L to 12.5 × 10 -3 . Mole/c cyanide ion. By such a reduced-type electroless silver plating solution, the decomposition of silver in the silver plating liquid is effectively prevented, and the stability of the liquid is improved, and the object to be plated such as the base metal is prevented from being excessively roughened, thereby being formed. Good coating properties, excellent appearance of the plating film.

〔實施例〕 [Examples]

以下，說明本發明的具體實施例。再者，本發明係不受下述的任一實施例所限定。 Hereinafter, specific embodiments of the present invention will be described. Furthermore, the present invention is not limited by any of the following embodiments.

<鍍液安定性及鍍敷皮膜評價> <Standing stability of plating solution and plating film evaluation>

調製下述所示的各自之還原型無電解鍍銀液。 The respective reduced-type electroless silver plating liquids shown below were prepared.

(實施例1) (Example 1)

使用苛性鈉，使含有銀濃度為9.0×10-3mol/L(1.0g/L)的硝酸銀、作為還原劑的羥基銨鹽(硫酸羥基銨)1.24×10-3mol/L、作為錯化劑的EDTA 0.15mol/L(50g/L)，更且添加氰化鉀1mg/L以使鍍液中的氰化物 離子濃度變成0.006×10-3mol/L之水溶液，成為pH9.0之還原型無電解鍍銀液。 Using caustic soda, silver nitrate containing a silver concentration of 9.0×10 -3 mol/L (1.0 g/L) and a hydroxylammonium salt (hydroxyammonium sulfate) as a reducing agent of 1.24×10 -3 mol/L were used as a mismatch. EDTA 0.15mol / L (50g / L), and added potassium cyanide 1mg / L to make the cyanide ion concentration in the plating solution into an aqueous solution of 0.006 × 10 -3 mol / L, to restore pH 9.0 Type electroless silver plating solution.

(實施例2) (Example 2)

除了添加氰化鉀300mg/L，以使鍍液中的氰化物離子濃度變成1.8×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except that potassium cyanide (300 mg/L) was added so that the cyanide ion concentration in the plating solution became 1.8 × 10 -3 mol/L.

(實施例3) (Example 3)

除了添加氰化鉀500mg/L，以使鍍液中的氰化物離子濃度變成3.0×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except that potassium cyanide (500 mg/L) was added so that the cyanide ion concentration in the plating solution was changed to 3.0 × 10 -3 mol/L.

(實施例4) (Example 4)

除了添加氰化鉀1000mg/L，以使鍍液中的氰化物離子濃度變成6.5×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except that potassium cyanide was added in an amount of 5,000 × 10 -3 mol/L.

(實施例5) (Example 5)

除了添加氰化鉀2000mg/L，以使鍍液中的氰化物離子濃度變成12.5×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except that the amount of cyanide ion in the plating solution was changed to 12.5 × 10 -3 mol/L.

(比較例1) (Comparative Example 1)

除了代替硝酸銀，添加銀濃度為9.0×10-3mol/L(1.0g/L)的氰化銀鉀，更添加氰化鉀300mg/L，以使鍍液中的合計氰化物離子濃度變成19.8×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 In addition to replacing silver nitrate, potassium silver cyanide having a silver concentration of 9.0×10 -3 mol/L (1.0 g/L) was added, and 300 mg/L of potassium cyanide was added to increase the total cyanide ion concentration in the plating solution to 19.8. A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except for ×10 -3 mol/L.

(比較例2) (Comparative Example 2)

除了代替硝酸銀，添加銀濃度為9.0×10-3mol/L(1.0g/L)的氰化銀鉀，不添加氰化鉀，使鍍液中的氰化物離子濃度變成18.0×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 In addition to replacing silver nitrate, silver silver cyanide with a silver concentration of 9.0×10 -3 mol/L (1.0 g/L) was added, and potassium cyanide was added without adding potassium cyanide to make the cyanide ion concentration in the plating solution 18.0×10 -3 mol. In the same manner as in Example 1, except for /L, a redox type electroless silver plating solution was prepared.

(比較例3) (Comparative Example 3)

除了不添加氰化鉀以外，與實施例1同樣地，調製還原型無電解鍍銀液。即，調製無氰的還原型無電解鍍銀液。 A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except that potassium cyanide was not added. That is, a reduction-free electroless silver plating solution having no cyanide is prepared.

(比較例4) (Comparative Example 4)

除了添加氰化鉀2100mg/L，以使鍍液中的氰化物離子濃度變成13.0×10-3mol/L以外，與實施例1同樣地，調製還原型無電解鍍銀液。 A redox type electroless silver plating solution was prepared in the same manner as in Example 1 except that potassium cyanide 2100 mg/L was added so that the cyanide ion concentration in the plating solution became 13.0 × 10 -3 mol/L.

其次，使用如以上所調製的還原型無電解鍍銀液，以BGA基板(上村工業股份有限公司製)作為被鍍物，施予還原型無電解鍍銀。 Then, a reduced-type electroless silver plating solution prepared as described above was used, and a BGA substrate (manufactured by Uemura Kogyo Co., Ltd.) was used as a material to be plated, and reduced electroless silver plating was applied.

再者，於還原型無電解鍍銀處理之前，作為前處理， 依順序進行下述表1中所示的各步驟。即，對於被鍍物的BGA基板，藉由ACL-738(上村工業股份有限公司製)的清潔劑處理(脫脂)後，藉由100g/L的過硫酸鈉溶液(SPS)進行軟蝕刻處理。接著，用10%硫酸(H2SO4)溶液來去除蝕刻殘液(酸洗)，在3%硫酸溶液中預浸處理後，用MNK-4(上村工業股份有限公司製)給予Pd觸媒(催化劑)。然後，使用無電解鎳液NPR-4(上村工業股份有限公司製)及無電解鈀液TPD-30(上村工業股份有限公司製)，形成基底之金屬皮膜。 Further, each step shown in Table 1 below was carried out in order as a pretreatment before the reduction type electroless silver plating treatment. In other words, the BGA substrate of the object to be plated was subjected to a soft etching treatment by a 100 g/L sodium persulfate solution (SPS) after being treated (degreased) with a detergent of ACL-738 (manufactured by Uemura Kogyo Co., Ltd.). Next, the etching residue (acid washing) was removed with a 10% sulfuric acid (H 2 SO 4 ) solution, and pre-impregnated in a 3% sulfuric acid solution, and then Pd catalyst was administered by MNK-4 (manufactured by Sakamura Kogyo Co., Ltd.). (catalyst). Then, an electroless nickel liquid NPR-4 (manufactured by Uemura Kogyo Co., Ltd.) and an electroless palladium liquid TPD-30 (manufactured by Uemura Kogyo Co., Ltd.) were used to form a base metal film.

無電解鍍銀處理係藉由在60℃將被鍍物浸漬於上述還原型無電解鍍銀液中20分鐘而進行。而且，在進行鍍敷處理後，在60℃升溫放置100小時，藉由鍍液的有無自分解，評價鍍液的安定性，以及鍍敷皮膜的焊接合強度及外觀。下述的表2中顯示其評價結果。 The electroless silver plating treatment was carried out by immersing the object to be plated in the reduced electroless silver plating solution at 60 ° C for 20 minutes. Further, after the plating treatment, the temperature was allowed to stand at 60 ° C for 100 hours, and the stability of the plating solution and the weld strength and appearance of the plating film were evaluated by the presence or absence of self-decomposition of the plating solution. The evaluation results are shown in Table 2 below.

再者，鍍敷皮膜之焊接合強度，係以在240℃-1次迴焊的處理來評價，將焊料斷裂模型為20個中16個以上時評價為接合強度良好(○)，將未達16個時評價為接合強度不良(×)。又鍍敷皮膜的外觀係以目視鍍銀皮膜的膜厚0.5μm時之外觀來確認。 In addition, the welding strength of the plating film was evaluated by the treatment at 240 ° C -1 reflow, and when the solder fracture model was 16 or more of 20, it was evaluated that the bonding strength was good (○), and the bonding strength was not reached. The 16 times were evaluated as poor joint strength (x). Further, the appearance of the plating film was confirmed by visually observing the appearance of the silver plating film at a film thickness of 0.5 μm.

如表2中所示，於鍍液中的氰化物離子濃度經控制在0.006×10-3mol/L~12.5×10-3mol/L的範圍中之實施例1~5的還原型無電解鍍銀液中，鍍液中的銀不分解，顯示良好的液安定性。又，於此等實施例1~5中，焊料接合強度 強，可形成具有良好的皮膜特性之鍍敷皮膜。再者，其所形成的鍍敷皮膜亦白色銀，具有漂亮的外觀。 As shown in Table 2, the reduction type cyanide ion concentration in the plating solution was controlled in the range of 0.006 × 10 -3 mol / L to 12.5 × 10 -3 mol / L of the reduced type electroless of Examples 1 to 5. In the silver plating solution, the silver in the plating solution does not decompose, indicating good liquid stability. Further, in Examples 1 to 5, the solder joint strength was strong, and a plating film having excellent film properties could be formed. Furthermore, the plating film formed is also white silver and has a beautiful appearance.

另一方面，於鍍液中的氰化物離子濃度各自為19.8×10-3mol/L、18.0×10-3mol/L、13.0×10-3mol/L的比較例1、2、4之還原型無電解鍍銀液中，雖然由於鍍液中的過剩之游離氰而防止銀的分解，但形成焊料接合強度弱，皮膜特性差的鍍敷皮膜。茲認為此係因為鍍液中存在的過剩之游離氰，過度地溶解基底金屬而使粗化。 On the other hand, the cyanide ion concentrations in the plating solution were respectively 19.8 × 10 -3 mol / L, 18.0 × 10 -3 mol / L, and 13.0 × 10 -3 mol / L of Comparative Examples 1, 2, and 4 In the reduced electroless silver plating solution, the decomposition of silver is prevented by excessive free cyanide in the plating solution, but a plating film having weak solder joint strength and poor film properties is formed. It is considered that this is because the excess free cyan present in the plating solution excessively dissolves the base metal to be roughened.

又，於鍍液中不含有氰的無氰之比較例3的還原型無電解鍍銀液中，雖然形成焊料接合強度強，具有良好的皮膜特性之鍍敷皮膜，但由於不含有氰而鍍液中的銀分解，無法確保液的安定性。再者，於此比較例3之使用還原型無電解鍍銀液時，形成帶黃色調的黃色銀之鍍敷皮膜，成為極不良的外觀。 Further, in the reduced electroless silver plating liquid of Comparative Example 3 which does not contain cyanide in the plating solution, a plating film having a strong solder joint strength and having excellent film properties is formed, but plating is performed without containing cyanide. The decomposition of silver in the liquid does not ensure the stability of the liquid. Further, in the case of using the reduced electroless silver plating solution of Comparative Example 3, a yellow silver-plated plating film was formed, which was an extremely poor appearance.

由以上的結果得知，藉由使鍍液中的氰化物離子濃度成為0.006×10-3mol/L~12.5×10-3mol/L之範圍，抑制銀的分解而維持液的安定性，同時析出形成白色銀之漂亮的銀，可形成外觀優異的皮膜。再者，得知藉由使氰化物離子成為上述濃度範圍，防止鍍敷基底金屬材料等被過剩地粗化，能形成具有良好的皮膜特性之鍍敷皮膜。 From the above results, it is known that the cyanide ion concentration in the plating solution is in the range of 0.006 × 10 -3 mol / L to 12.5 × 10 -3 mol / L, thereby suppressing the decomposition of silver and maintaining the stability of the liquid. At the same time, a beautiful silver which forms white silver is precipitated, and a film having an excellent appearance can be formed. Further, it has been found that by causing the cyanide ion to have the above concentration range, the plating base metal material or the like is prevented from being excessively coarsened, and a plating film having excellent film properties can be formed.

<關於還原劑> <About reducing agent>

其次，如上述實施例1~5，於氰化物離子濃度經控制在0.006×10-3mol/L~12.5×10-3mol/L之範圍的還原型無電 解鍍銀液中，檢討較佳的還原劑。再者，實驗係以上述實施例2之組成作為基本組成進行。 Next, as in the above Examples 1 to 5, in the reduction type electroless silver plating solution in which the cyanide ion concentration is controlled in the range of 0.006 × 10 -3 mol / L to 12.5 × 10 -3 mol / L, the evaluation is preferred. Reducing agent. Further, the experiment was carried out by using the composition of the above Example 2 as a basic composition.

(實施例6) (Example 6)

除了添加作為還原劑的肼(硫酸肼)1.24×10-3mol/L以外，與實施例2同樣地，調製氰化物離子濃度為0.006×10-3mol/L的還原型無電解鍍銀液。 A reduced-type electroless silver plating solution having a cyanide ion concentration of 0.006 × 10 -3 mol/L was prepared in the same manner as in Example 2 except that ruthenium (ruthenium sulfate) as a reducing agent was added at 1.24 × 10 -3 mol/L. .

(實施例7) (Example 7)

除了添加作為還原劑的甲醛1.24×10-3mol/L以外，與實施例2同樣地，調製氰化物離子濃度為0.006×10-3mol/L的還原型無電解鍍銀液。 A reduced-type electroless silver plating solution having a cyanide ion concentration of 0.006 × 10 -3 mol/L was prepared in the same manner as in Example 2 except that 1.24 × 10 -3 mol/L of formaldehyde as a reducing agent was added.

使用上述實施例2及實施例6及7中調製的還原型無電解鍍銀液，調查鍍銀皮膜的膜厚相對於鍍敷時間之關係。圖1中顯示改變還原劑時，膜厚相對於鍍敷時間之測定結果的曲線圖。 Using the reduced electroless silver plating solution prepared in the above Example 2 and Examples 6 and 7, the relationship between the film thickness of the silver plating film and the plating time was examined. Fig. 1 is a graph showing the measurement results of the film thickness with respect to the plating time when the reducing agent is changed.

如圖1中所示，可知於使用羥基銨鹽作為還原劑的實施例2之無電解鍍銀液中，由於延長鍍敷時間而得之鍍銀皮膜的膜厚亦略直線地變厚，由於還原反應而銀析出，形成皮膜。另一方面，可知於使用肼或甲醛作為還原劑的實施例6及7中，若經過規定的時間，則其以後係膜厚係不太變厚。茲認為此係因為在肼或甲醛中，藉由還原反應而使銀析出，但另一方面，由於取代反應的因素亦大幅作用，基底金屬稍微地溶解。 As shown in Fig. 1, it is understood that in the electroless silver plating solution of Example 2 using a hydroxyammonium salt as a reducing agent, the film thickness of the silver plating film which is obtained by prolonging the plating time is also slightly thicker, because The reduction reaction and silver are precipitated to form a film. On the other hand, in Examples 6 and 7 in which hydrazine or formaldehyde was used as the reducing agent, it was found that the thickness of the film was not too thick after a predetermined period of time elapsed. It is considered that this is because silver is precipitated by reduction reaction in hydrazine or formaldehyde, but on the other hand, the base metal is slightly dissolved due to a large effect of the substitution reaction.

由此可知，於氰化物離子濃度經控制在0.006×10-3mol/L~12.5×10-3mol/L之範圍的還原型無電解鍍銀液中，藉由使用硫酸羥基銨或醋酸羥基銨等的羥基銨鹽作為還原劑，可更有效地進行還原反應，不發生取代反應所致的基底金屬之溶解，可形成具有良好的皮膜特性之鍍敷皮膜。 It can be seen that in the reduced electroless silver plating solution whose cyanide ion concentration is controlled in the range of 0.006×10 -3 mol/L to 12.5×10 -3 mol/L, by using ammonium hydroxysulfate or hydroxyl acetate As a reducing agent, a hydroxyammonium salt such as ammonium can be more effectively subjected to a reduction reaction, and dissolution of a base metal due to a substitution reaction does not occur, and a plating film having good film properties can be formed.

圖1係顯示改變還原劑時，鍍敷皮膜的膜厚相對於鍍敷時間的關係之曲線圖。 Fig. 1 is a graph showing the relationship between the film thickness of a plating film and the plating time when the reducing agent is changed.

Claims (4)

一種還原型無電解鍍銀液，其係含有水溶性銀鹽與還原劑之還原型無電解鍍銀液，其特徵係含有0.006×10-3mol/L~12.5×10-3mol/L的氰化物離子，上述還原劑係由硫酸羥基銨、醋酸羥基銨中選出的1種以上者。 A reduced electroless silver plating solution, which is a reduced electroless silver plating solution containing a water-soluble silver salt and a reducing agent, and is characterized by containing 0.006×10 -3 mol/L to 12.5×10 -3 mol/L. The cyanide ion is one or more selected from the group consisting of hydroxylammonium sulfate and ammonium hydroxyacetate. 如申請專利範圍第1項之還原型無電解鍍銀液，其中上述水溶性銀鹽係氰化合物以外之銀鹽，上述氰化物離子係作為鹼金屬氰化物含有。 The reduced electroless silver plating solution according to the first aspect of the invention, wherein the water-soluble silver salt is a silver salt other than the cyanide compound, and the cyanide ion is contained as an alkali metal cyanide. 如申請專利範圍第1或2之還原型無電解鍍銀液，其係pH為8~11者。 For example, the reduced electroless silver plating solution of Patent No. 1 or 2 is a pH of 8 to 11. 一種還原型無電解鍍銀方法，其係使用如申請專利範圍第1項之還原型無電解鍍銀液，對被鍍物施予無電解鍍銀。 A reduced electroless silver plating method which uses an electroless silver plating solution according to claim 1 of the patent application, and applies electroless silver plating to the object to be plated.
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